CN114057669A - Ethylene epoxidation constant-temperature driving method - Google Patents
Ethylene epoxidation constant-temperature driving method Download PDFInfo
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- CN114057669A CN114057669A CN202010743456.2A CN202010743456A CN114057669A CN 114057669 A CN114057669 A CN 114057669A CN 202010743456 A CN202010743456 A CN 202010743456A CN 114057669 A CN114057669 A CN 114057669A
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- 238000000034 method Methods 0.000 title claims abstract description 72
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000005977 Ethylene Substances 0.000 title claims abstract description 61
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000001301 oxygen Substances 0.000 claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 37
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052702 rhenium Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 6
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003750 ethyl chloride Drugs 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 3
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- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 3
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000001553 barium compounds Chemical class 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 150000003438 strontium compounds Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 150000003298 rubidium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention belongs to the field of ethylene oxide preparation, and relates to an ethylene epoxidation constant-temperature driving method. The method comprises the following steps: introducing feed gas containing ethylene, oxygen and a regulator at a constant reaction temperature of 200-230 ℃ in the presence of a high-selectivity silver catalyst for ethylene epoxidation, and starting the ethylene epoxidation to generate ethylene oxide; the whole reaction starting process comprises three stages, wherein the first stage is 0-T1Time period, the second stage is T1‑T2Time period, the third phase is T2To the end of the reaction start-up process, wherein T1At 12-24 hours, T272-96 hours; the amount of the regulator added was in the range of 0.1ppm to 10ppm throughout the start-up of the reaction. The method adopts a constant-temperature driving mode, greatly reduces the temperature operation requirement in the reaction starting process, can fully utilize the reaction heat generated by the reaction, and can effectively avoid the temperature runaway problem caused by overhigh initial activity of the high-selectivity catalyst.
Description
Technical Field
The invention belongs to the field of ethylene oxide preparation, and particularly relates to an ethylene epoxidation constant-temperature driving method.
Background
Ethylene oxide is an important organic chemical product as a derivative monomer of ethylene, and accounts for the worldwide ethylene consumption distribution of ethylene derivatives second to polyethylene and polyvinyl chloride. In the industrial process of producing ethylene oxide by ethylene epoxidation, raw material gas containing components such as ethylene, oxygen and the like is used for producing ethylene oxide under certain reaction conditions under the action of a silver catalyst, and byproducts such as carbon dioxide, water and the like are generated at the same time. The activity, selectivity and stability of the silver catalyst used therein are three main performance indexes, determine the reaction cost and directly influence the economic benefit.
The ethylene oxidation process can be divided into two processes of selective oxidation (partial oxidation) and deep oxidation (complete oxidation), wherein carbon-carbon double bonds (C ═ C) in ethylene molecules have outstanding unsaturation, the selective oxidation of the carbon-carbon double bonds can be realized under certain oxidation conditions to generate ethylene oxide, and the deep oxidation is easy to generate carbon dioxide and water under normal conditions, wherein the side reaction is a main side reaction, and the reaction heat is dozens of times of the main reaction, so that the control is required, on one hand, the runaway of the reaction caused by strong heat release is prevented, the safety production of the device is endangered, and the unit consumption of the product is reduced. For this reason, the preparation of an acceptable high-performance catalyst and the strict control of certain process conditions are key to prevent the increase of side reactions.
There are three different types of silver catalysts that are mainly used by industrial EO/EG production plants: the catalyst is a high-activity silver catalyst, and the catalyst has high activity, good stability and 80-82% selectivity; secondly, the silver catalyst with high selectivity is used, and the highest selectivity of the catalyst reaches more than 88 percent; and third is a medium selectivity silver catalyst (both activity and selectivity are between the first two). The adoption of silver catalysts with higher selectivity is a trend, and the higher selectivity means that the effective utilization rate of carbon atoms is higher, the emission of carbon dioxide is lower, the production cost of the device is lower, and the market competitiveness and social benefits are higher.
The continuous innovation and optimization of the catalyst preparation are one aspect, and on the other hand, the optimization of the process conditions is also the key direction of research. The start-up of the reaction of the catalyst is the first step of the whole reaction process and is also the most important one.
For start-up for highly selective catalysts, US 20090281339 discloses: in the reactor, a highly selective epoxidation catalyst is contacted with raw materials of ethylene, oxygen and an organic chloride (vinyl chloride) for a period of time, and the reactor outlet gas is detected until at least 1X 10 is detected in the reactor outlet gas or the recycle gas-5The mol% vinyl chloride is increased and the amount of chloride in the feed is subsequently adjusted to a value sufficient for substantially optimum selectivity to ethylene oxide.
For a start-up method for an ethylene epoxidation process, CN 101711239B provides a method for achieving a controlled start-up temperature of the epoxidation process, which is higher than the highest reactor temperature that can be achieved by using an external heat source, in the temperature range of about 240 ℃ to 290 ℃. The process utilizes the internal heat of reaction in the reactor to bring the bed temperature and reactor temperature to a temperature suitable for conditioning the highly selective catalyst.
CN 102666514B describes a process for starting the epoxidation of ethylene. The method comprises the following steps: by introducing a feed gas consisting of ethylene and oxygen in the presence of an epoxidation catalyst at a temperature in the range of from 180 ℃ to 210 ℃. And adding about 0.05 to 2ppm of a moderator to the feed gas; the first temperature is raised to a second temperature of 240 ℃ -250 ℃ for about 12 hours to 60 hours and held for about 50 hours to 150 hours.
CN 102666515B provides a start-up method for an ethylene epoxidation process. Comprises initiating a reaction of a feed gas comprising ethylene and oxygen at a first temperature of 180 ℃ to 210 ℃, maintaining the first temperature for a period of 6 to 50 hours and raising the temperature to a second temperature of 230 ℃ to 290 ℃. At this time, a sufficient concentration of the modifier is added such that the amount of the modifier adsorbed on the catalyst after the second temperature is reached is about 10 to 50g/m3A catalyst; continuing to maintain the second temperature for a period of time ranging from about 50 hours to about 350 hours while adding from 0.5% to 25% carbon dioxide to the feed gas; the second temperature is decreased to a third temperature while the moderator concentration is increased.
CN 103261178A describes a process for starting up a high efficiency alkylene oxide catalyst. The method comprises the step of enabling a feed gas containing olefin, oxygen and at least one organic chloride to react on a high-efficiency silver catalyst, so that the ethylene oxide/m is not more than 0.03kT after the reactor is put into operation for the first time3The reaction temperature is 215 ℃ to 240 ℃ and the molar ratio of oxygen to ethylene in the feed gas is at least 0.2 over the catalyst aging period of the catalyst.
The high-concentration series silver catalyst requires acclimation for a certain time at the initial start of the start and has the characteristic of high initial activity. In addition, in practical industrial application, the driving method is different for different types of high-selectivity silver catalysts and different working conditions. Therefore, a proper start-up method needs to be designed aiming at the characteristics of the high-concentration series silver catalyst at the initial start-up stage. On the basis of stable operation, the activity of the catalyst is effectively controlled, and the selectivity of the catalyst is quickly raised. The optimization of the initial process conditions lays a foundation for the long-term stable and efficient operation of the catalyst. Therefore, it is very meaningful to develop a start-up method that can protect the high-concentration silver catalyst and optimize the operating conditions of the catalyst.
In the process of ethylene epoxidation, flexible adjustment of temperature is an important adjustment means, but for many small-scale enterprises or limited by specific reaction requirements, adjustment of reactor temperature cannot be realized, so that start-up can only be carried out at constant temperature, which presents a technical problem for smooth start-up of an ethylene epoxidation process adopting a high-selectivity silver catalyst. Therefore, there is a need to develop a method for starting up a high-selectivity silver catalyst at constant temperature to meet the actual industrial demands of these enterprises.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a constant temperature start-up method for ethylene epoxidation.
Specifically, the invention provides an ethylene epoxidation constant-temperature driving method, which comprises the following steps:
introducing feed gas containing ethylene, oxygen and a regulator at a constant reaction temperature of 200-230 ℃ in the presence of a high-selectivity silver catalyst for ethylene epoxidation, and starting the ethylene epoxidation to generate ethylene oxide;
the whole reaction starting process comprises three stages, wherein the first stage is 0-T1Time period, the second stage is T1-T2Time period, the third phase is T2To the end of the reaction start-up process, wherein T1At 12-24 hours, T272-96 hours; the amount of the regulator added was in the range of 0.1ppm to 10ppm throughout the start-up of the reaction.
The 0 time point of the first stage is the time point at which the start of the reaction is initiated, T1、T2The time point is counted from the time point at which the start of the reaction is started.
The constant-temperature start refers to that the temperature is always constant within a certain constant value within a temperature range of 200 ℃ to 230 ℃ in the whole start process.
The concept of high selectivity silver catalyst as referred to in the present invention is well known to those skilled in the art and refers to silver catalysts having a selectivity of 85-88%. Because the high-concentration series silver catalyst has the characteristics of high initial activity, a certain time acclimation period and the like, the driving process needs to be matched with the characteristics. In addition, under the requirement of constant-temperature start, the invention achieves the optimal process condition by adjusting the adding amount of oxygen, ethylene and regulator in the whole start-up start process, thereby realizing smooth start.
According to the process of the invention, it is preferred that the regulator is added in the first stage in an amount CT1Addition C higher than in the second stageT2More preferably, CT2And CT1Difference of (a) CT0.1-1 ppm; preferably, the regulator is added in the second and third stages in such an amount that the catalyst selectivity S remains equal to or greater than 80%. Because the temperature needs to be constant, in the process of gradually increasing the inlet oxygen concentration, the start-up stability needs to be maintained through the regulator, when the selectivity S of the catalyst is lower than 80%, the amount of the regulator is properly increased until the selectivity S is larger than or equal to 80%, and the inlet oxygen concentration can not be continuously and gradually increased.
The selectivity S in the present invention is calculated by continuously measuring the reactor inlet and outlet gas compositions on-line using methods well known in the art. The measurement results were corrected for volume shrinkage, and the selectivity (S) was calculated according to the following formula:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2Is the difference in carbon dioxide concentration between the reactor outlet gas and the inlet gas.
The regulator in the method of the invention can be various inhibitors commonly used in ethylene epoxidation reaction, and can be specifically selected from organic halogenated hydrocarbon compounds; preferably, the modifier is selected from at least one of methyl chloride, ethyl chloride and vinyl chloride. The methyl chloride is, for example, methyl chloride, methylene chloride, the ethyl chloride is, for example, ethyl chloride, ethylene dichloride, and the vinyl chloride is, for example, vinyl chloride, ethylene dichloride.
According to the process of the present invention, the amount of ethylene used is adjusted according to the reaction stage. Preferably, in the first stage and the second stage, the content of ethylene in the feed gas is maintained between 1 mol% and 15 mol%, based on the total molar amount of feed gas; in a third stage, the content of ethylene in the feed gas is gradually increased to a set value; the set value is preferably from 28 mol% to 30 mol%, based on the total molar amount of feed gas.
According to the process of the present invention, the amount of oxygen used is adjusted according to the reaction stage. Preferably, in the first stage, the content of oxygen in the feed gas is gradually increased from 0 to CO1Further increased to C in the second stageO2Further increased to or maintained at the set value, C, during the third phaseO11 mol% -1.5 mol%, CO2From 5 mol% to 7.5 mol%, based on the total molar amount of feed gas.
In the whole reaction start-up process, firstly controlling the inlet oxygen concentration not to exceed 1.5 mol%, stabilizing the ethylene concentration to be 15 mol%, and properly increasing the addition of EDC until the outlet oxygen concentration of the reactor; when the selectivity S of the catalyst is lower than 80%, the operation is optimized, and the inlet oxygen concentration cannot be continuously and gradually increased until the selectivity S is more than or equal to 80%. The oxygen concentration was increased by 0.2 to 0.8 mol% per 4 hours. Gradually increase to a set value (e.g., 7.5 mol%); after the oxygen concentration reaches the set point, if the EO concentration does not reach the set point, the inlet ethylene concentration may be gradually increased to the set point (e.g., 28 mol%) at a rate of 1-2 mol% increase per 4 hours.
According to the present invention, it is preferable that the concentration of carbon dioxide be maintained less than 3 mol% throughout the start-up of the reaction, and the fluctuation range in the second stage and the third stage be not more than 1 mol% based on the total molar amount of the feed gas. At the beginning, the concentration of carbon dioxide is continuously accumulated along with the reaction, and when the reaction is continued and the concentration of carbon dioxide is continuously increased, carbon dioxide can be discharged or increased according to the requirement so as to keep the concentration in the range.
According to the invention, it is preferred to maintain the selectivity between 85% and 90% during the second and third stages (during the maintaining step).
In the method of the present invention, the total time period of the whole reaction start-up process can be 120-144 hours.
The ethylene epoxidation constant-temperature start-up method is applicable to various high-selectivity silver catalysts, and generally, the high-selectivity silver catalyst comprises an alpha-alumina carrier and the following components loaded on the carrier: silver, an alkali metal promoter, an alkaline earth metal promoter, a rhenium promoter and optionally a rhenium synergist.
Further, the silver content is 1 to 35 wt%, preferably 15 to 30 wt%, based on the total weight of the catalyst.
In the highly selective silver catalyst used in the present invention, the alkali metal promoter may be at least one of a lithium compound, a sodium compound, a potassium compound, a rubidium compound and a cesium compound, such as a nitrate, a sulfate or a hydroxide of these alkali metals, preferably cesium sulfate and/or cesium nitrate. The silver catalyst has an alkali metal content, calculated as alkali metal element, of 5 to 2000ppm, preferably 10 to 1500ppm, based on the total weight of the catalyst.
In the highly selective silver catalyst used in the present invention, the alkaline earth metal promoter may be at least one of a magnesium compound, a calcium compound, a strontium compound and a barium compound, such as an oxide, sulfate, nitrate, oxalate or acetate of these alkaline earth metals, or a combination of any two or more of the foregoing compounds, preferably a barium compound and/or a strontium compound, more preferably barium acetate and/or strontium acetate. The silver catalyst has an alkaline earth metal content, calculated as alkaline earth metal element, of from 5 to 2200ppm, preferably from 10 to 1500ppm, based on the total weight of the catalyst.
In the highly selective silver catalyst used in the present invention, the rhenium promoter may be at least one of rhenium oxide, perrhenic acid and perrhenate, preferably ammonium perrhenate and/or cesium perrhenate. The rhenium promoter content in the silver catalyst, calculated as rhenium element, is from 5 to 1500ppm, preferably from 10 to 1000ppm, based on the total weight of the catalyst.
In the highly selective silver catalyst used in the present invention, the optional rhenium promoter co-promoter may be a compound of any one of the transition metals of the periodic table of the elements, or a mixture of several transition metal compounds, preferably at least one selected from the group consisting of: oxyacids of group VI B and group VII B transition metal elements and salts thereof, for example, tungstic acid, cesium tungstate, molybdic acid, ammonium molybdate and the like. The content of the co-promoter in the silver catalyst, calculated as the co-promoter element, is from 0 to 1000ppm, preferably from 10 to 500ppm, based on the total weight of the catalyst.
The high selectivity silver catalyst can be prepared by adopting a conventional method in the field. For example, the alumina support is impregnated with an impregnation liquid. The alumina carrier is preferably a porous alpha-alumina carrier, and further preferably has the following characteristics: alpha-alumina content is more than or equal to 90 wt%, and specific surface area is 0.8-3.0m2(iii) per gram, pore volume of 0.3-0.8ml/g, water absorption of 30-70%, and crush strength of 50-200N per pellet.
In the invention, the specific surface area of the carrier is measured by adopting a nitrogen physical adsorption BET method, the pore volume is measured by adopting a mercury intrusion method, the water absorption is measured by adopting a density method, the side pressure strength is measured by adopting a DL II type intelligent particle strength tester, a carrier sample is selected, and the radial crushing strength is measured and then an average value is taken to obtain the carrier.
The alpha-alumina carrier used in the present invention can also be prepared by a method conventional in the art.
According to the start-up method for the high-selectivity silver catalyst in the process of preparing the ethylene oxide by starting the epoxidation of the ethylene, provided by the invention, the device is kept to operate at a constant temperature within a temperature range from about 200 ℃ to about 230 ℃ all the time in the start-up process of the catalyst. The method adopts a constant-temperature starting mode, so that the temperature operation requirement in the reaction starting process is greatly reduced, and the method adopting constant-temperature starting at a lower temperature can not only fully utilize the reaction heat generated by the reaction, but also effectively avoid the temperature runaway problem caused by overhigh initial activity of the high-selectivity catalyst, thereby achieving two purposes at one stroke. Meanwhile, under the condition of no requirement of rapid load rise, the reaction temperature is kept constant, and the mild and stable reaction is more facilitated. The continuous and stable temperature environment is beneficial to the acclimatization of the catalyst in the early reaction stage.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
In the following examples, the ethylene epoxidation reaction was measured on-line by mass spectrometry and other detection means to continuously measure the reactor inlet and outlet gas compositions. The measurement results were corrected for volume shrinkage, and the selectivity (S) was calculated according to the following formula:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2Is the difference in carbon dioxide concentration between the reactor outlet gas and the inlet gas.
Preparation example 1
This preparation example is used to illustrate the highly selective silver catalyst and the preparation method thereof used in the examples of the present invention.
(1) Preparation of high-selectivity silver catalyst carrier
Mixing 50-200 mesh trihydrate alpha-Al2O3450g and 200-mesh 500-mesh pseudo-monohydrate Al2O3100g of the mixture is put into a blender to be mixed evenly. Then transferring the mixture into a kneader, dissolving 10.5g of ammonium fluoride into 120 ml of dilute nitric acid solution with the mass ratio of nitric acid to water being 1: 3, pouring the solution into the kneader, and kneading the mixture into paste capable of being extruded and molded. Extruding to form a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 60-120 deg.C for 3 hr to reduce the free water content to below 10 wt% to obtain a green body. Then the green body is put into an electric furnace and is heated from room temperature to 1410-1450 ℃ for 30 hours, and the temperature is kept constant for 2 hours to obtain white porous alpha-Al2O3A carrier sample.
The obtained porous alpha-Al2O3The vector is characterized as follows: alpha-A12O3The content is more than 90 percent, and the crushing strength is 20-200N/grain; the specific surface area is 0.2-3.0m2(ii)/g; the water absorption rate is not lower than 30%; the pore volume is 0.30-0.85 ml/g.
(2) Preparation of high-selectivity silver catalyst
Firstly, reacting silver nitrate water solution with ammonium oxalate or oxalic acid water solution to separate out silver oxalate precipitate, filtering, washing with deionized water until no nitrate ions exist, then dissolving the silver oxalate into a mixed solution of ethylenediamine and ethanolamine, and adding an auxiliary agent and urea to prepare a silver-ammonia impregnation solution. The above alumina support was then impregnated with the obtained impregnation solution, drained, and kept in an air stream at a temperature in the range of 400 ℃ for 10 minutes to perform thermal decomposition.
The silver catalyst produced contained 28% silver, 100ppm alkali metal, 100ppm alkaline earth metal and 600ppm rhenium based on its total weight.
Example 1
The start-up reaction was started using the high selectivity silver catalyst prepared in preparation example 1. The method comprises the following steps:
1. preparation before oxygen feeding: before oxygen introduction, nitrogen is introduced into the reactor for replacement, so that the oxygen content in the gas leaving the reactor is less than 0.5 mol%. When the oxygen content in the replacement gas leaving the reactor is less than 0.5 mol%, filling nitrogen to increase the pressure of the reactor to 1.8-1.9 MPa. And the catalyst bed temperature was maintained at 200 c using the plant heating equipment.
2. Preparing for oxygen feeding: the temperature of the device is constant at 218 ℃, and the system pressure is about 2.1MPa and C2H4The concentration is 15.0 mol%, and the stability is kept.
3. The oxygen addition reaction was carried out under the specific conditions shown in the pilot plant start-up schedule (table 1):
the first stage is as follows: the inhibitor EDC was added to the recycle gas at a substantially constant temperature, pressure and ethylene concentration, and oxygen was added after 10 minutes. The oxygen feeding speed is slow, and the inlet gas O is gradually increased2The concentration reaches between 0.5 and 1.0mol percent and is kept for 1 to 2 hours. The oxygen concentration is then increased and the inhibitor addition is adjusted so that oxygen is present at the reactor outlet.
And a second stage: keeping the concentration of ethylene unchanged, gradually increasing the oxygen concentration, adjusting the content of the inhibitor when the selectivity S of the catalyst is lower than 80 percent until the selectivity S is more than or equal to 80 percent, and then continuously and gradually increasing the inlet oxygen concentration to 7.5mol percent. The oxygen concentration was increased at a rate of 0.5 mol% per 4 hours.
And a third stage: when the oxygen concentration of the system reached 7.5%, the ethylene concentration was gradually increased to the set value of 28 mol% under the condition that the reaction was stable, and the rate of increase was 1.5 mol% per 4 hours, thereby increasing the outlet EO concentration to the set value (1% -3%).
TABLE 1 Pilot plant device Start-Up operation reference timetable
Example 2
The YS series high-selectivity silver catalyst is applied to a certain factory. The reactor is filled with nitrogen for replacement before the device is started, so that the oxygen content in the replacement gas leaving the reactor is less than 0.5 percent; the temperature of the reactor is raised to 218 ℃, and the charging start-up condition is met.
Firstly, feeding ethylene to 15 mol% in a device system; the regulator dichloroethane (EDC) was added to the system at a rate of 1500g/h 10 minutes prior to the oxygen addition to the unit. After the oxygen feeding preparation work is finished, a small distributor is opened, oxygen is added into the system by using the minimum oxygen feeding amount, and the reaction is successful once after the oxygen feeding. The catalyst activity was high in the initial 0-24 hours of the reaction, and the addition of a large amount of EDC was effective in controlling the catalyst activity, at which time the total chlorine in the system was about 5.0 ppm. Optimizing the system within 24-72 hours, gradually reducing the addition of the regulator, and controlling the total chlorine in the system to be about 4.0 ppm; the load of the device is gradually increased, the oxygen feeding amount is increased, the oxygen concentration is gradually increased to about 5 mol%, the selectivity of the catalyst begins to gradually increase, and the average selectivity exceeds 83%. After 72-120 hours, the device switches to a large distributor for oxygen feeding and switches to methane stabilization along with the increase of the load. Increasing the oxygen concentration of the system load to 7.5 percent and the ethylene load to 28 percent; the total chlorine of the system is controlled at about 2.0-3.0 ppm. After 120 hours, the catalyst was acclimatized, oxygen and ethylene concentrations were maintained, drum temperature was maintained constant, and chloride addition continued to be optimized to about 2.5 ppm.
Finally, the catalyst reaction temperature was constantly controlled at about 218 ℃ and the total chlorine was maintained at about 2.5 ppm. Ethylene was fed at 3.6 tons/hour and oxygen at 3.85 tons/hour. The ethylene concentration is 27.61%, the oxygen concentration is 8.35%, the carbon dioxide concentration is 1.82%, and the outlet EO is 2.23%. Average selectivity 85.2%, feed selectivity 86.47%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. An ethylene epoxidation constant-temperature start-up method comprises the following steps:
introducing feed gas containing ethylene, oxygen and a regulator at a constant reaction temperature of 200-230 ℃ in the presence of a high-selectivity silver catalyst for ethylene epoxidation, and starting the ethylene epoxidation to generate ethylene oxide;
the whole reaction starting process comprises three stages, wherein the first stage is 0-T1Time period, the second stage is T1-T2Time period, the third phase is T2To the end of the reaction start-up process, wherein T1At 12-24 hours, T272-96 hours; the amount of the regulator added was in the range of 0.1ppm to 10ppm throughout the start-up of the reaction.
2. The method for the constant-temperature start-up of the epoxidation of ethylene according to claim 1, wherein the regulator is added in the first stage in an amount CT1Addition C higher than in the second stageT2Preferably, CT2And CT1Difference of (a) CT0.1-1 ppm; the regulator is added in the second stage and the third stage in such an amount that the selectivity S of the catalyst is maintained at 80% or more.
3. The ethylene epoxidation isothermal start-up method according to claim 1, wherein said regulator is selected from the group consisting of organic halogenated hydrocarbon compounds; preferably, the modifier is selected from at least one of methyl chloride, ethyl chloride and vinyl chloride.
4. The ethylene epoxidation constant temperature start-up method according to claim 1, wherein in the first stage and the second stage, the content of ethylene in the feed gas is maintained at 1 mol% to 15 mol%, based on the total molar amount of the feed gas;
in a third stage, the content of ethylene in the feed gas is gradually increased to a set value; the set value is preferably 28 mol% to 30 mol%, based on the total molar amount of the feed gas; the rate of increase of the ethylene content in the third stage is preferably increased by 1 to 2 mol% per 4 hours.
5. The ethylene epoxidation isothermal start-up method according to claim 1, wherein, in a first stage, the content of oxygen in the feed gas is gradually increased from 0 to CO1Further increased to C in the second stageO2Further increased to or maintained at the set value, C, during the third phaseO11 mol% -1.5 mol%, CO2From 5 mol% to 7.5 mol%, based on the total molar amount of feed gas; the oxygen content is preferably increased by 0.2 to 0.8 mol% per 4 hours.
6. The process for the isothermal start-up of the epoxidation of ethylene of claim 1, wherein the concentration of carbon dioxide is kept less than 3 mol% throughout the start-up of the reaction and the amplitude of the fluctuations in the second and third stages does not exceed 1 mol%, based on the total molar amount of feed gas.
7. The process for the isothermal start-up of the epoxidation of ethylene according to claim 1, wherein in the second stage and in the third stage a selectivity of 85% to 90% is maintained.
8. The method for constant-temperature start-up of ethylene epoxidation as claimed in claim 1, wherein the total time period of the whole reaction start-up process is 120-144 hours.
9. The ethylene epoxidation constant temperature start-up method according to any one of claims 1 to 8, wherein the high selectivity silver catalyst comprises an α -alumina carrier and supported thereon the following components: silver, an alkali metal promoter, an alkaline earth metal promoter, a rhenium promoter and optionally a rhenium synergist.
10. The process for the isothermal start-up of the epoxidation of ethylene according to claim 9, wherein the silver content is from 1 to 35 wt. -%, preferably from 15 to 30 wt. -%, based on the total weight of the catalyst; the content of the alkali metal is 5-2000ppm, preferably 10-1500 ppm; the content of the alkaline earth metal is 5-2200ppm, preferably 10-1500 ppm; the content of the rhenium auxiliary agent is 5-1500ppm, preferably 10-1000 ppm; the content of the rhenium synergistic auxiliary element is 0-1000ppm, preferably 10-500 ppm.
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