CN114057669B - Ethylene epoxidation constant-temperature driving method - Google Patents
Ethylene epoxidation constant-temperature driving method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 75
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000005977 Ethylene Substances 0.000 title claims abstract description 62
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000001301 oxygen Substances 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052709 silver Inorganic materials 0.000 claims abstract description 43
- 239000004332 silver Substances 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000000977 initiatory effect Effects 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910052702 rhenium Inorganic materials 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003750 ethyl chloride Drugs 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 101000872083 Danio rerio Delta-like protein C Proteins 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- -1 polyethylene Polymers 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000007864 aqueous solution Substances 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000008187 granular material Substances 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
- 238000005457 optimization Methods 0.000 description 2
- 239000000047 product 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
- 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
- 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
- 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
- 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
- 238000006073 displacement reaction Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 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
- 239000011259 mixed solution Substances 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
- 235000006408 oxalic acid Nutrition 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 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
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
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- 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 a constant-temperature driving method for ethylene epoxidation. Comprising the following steps: at a constant reaction temperature of 200-230 ℃, in the presence of a high-selectivity silver catalyst for ethylene epoxidation, introducing a feed gas containing ethylene, oxygen and a regulator, and starting the ethylene epoxidation to generate ethylene oxide; the whole reaction starting process comprises three stages, wherein the first stage is 0-T 1 Time period, the second stage is T 1 ‑T 2 Time period, the third stage is T 2 To the end of the reaction initiation process, wherein T 1 For 12-24 hours, T 2 72 to 96 hours; the amount of the regulator added ranges from 0.1ppm to 10ppm throughout the reaction initiation. The method of constant-temperature start-up is adopted, so that the temperature operation requirement in the reaction starting process is greatly reduced, the reaction heat generated by the reaction can be fully utilized, and the problem of temperature runaway caused by the over-high initial activity of the high-selectivity catalyst can be effectively avoided.
Description
Technical Field
The invention belongs to the field of ethylene oxide preparation, and particularly relates to a constant-temperature driving method for ethylene epoxidation.
Background
Ethylene oxide is an important organic chemical product as a derivative monomer of ethylene, and the ethylene derivative accounts for the second only of polyethylene and polyvinyl chloride in the world in terms of consumption distribution. In the industrial process of producing ethylene oxide by epoxidation of ethylene, raw material gas containing ethylene, oxygen and other components produces ethylene oxide under certain reaction conditions under the action of a silver catalyst, and byproducts such as carbon dioxide, water and the like are produced. The activity, selectivity and stability of the silver catalyst used are three main performance indexes, which determine the cost of the reaction and directly affect the economic benefit.
The ethylene oxidation process can be divided into two types of selective oxidation (partial oxidation) and deep oxidation (complete oxidation), carbon-carbon double bonds (C=C) in ethylene molecules have outstanding unsaturation, selective oxidation of carbon-carbon double bonds can be realized under certain oxidation conditions to generate ethylene oxide, and deep oxidation is easy to occur under normal conditions to generate carbon dioxide and water, wherein the side reaction is a main side reaction, and the reaction heat is ten times of that of the main reaction, so that the side reaction is controlled, 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 products is reduced. For this reason, the preparation of a qualified high-performance catalyst and the strict control of certain process conditions are key to preventing the increase of side reactions.
The silver catalysts mainly used in commercial EO/EG production facilities are of three different types: the catalyst has high activity, good stability and 80-82% selectivity; secondly, a high-selectivity silver catalyst, wherein the highest selectivity of the catalyst is more than 88%; third is a medium selectivity silver catalyst (both active and selective between the former two). The silver catalyst with higher selectivity is a trend, and the higher the selectivity means that the higher the effective utilization rate of carbon atoms is, the lower the carbon dioxide emission is, the lower the production cost of the device is, and the higher the market competitiveness and the social benefit are.
The continuous innovative optimization of catalyst preparation is one aspect, and on the other hand, the optimization of process conditions is also the key direction of research. The starting of the reaction of the catalyst is the first step of the whole reaction process and is the most important procedure.
For start-up for high selectivity catalysts, US 20090281339 discloses: in the reactor, the high selectivity epoxidation catalyst is contacted with the feed ethylene, oxygen and organochlorine (vinyl chloride) for a period of time and the reactor outlet gas is detected until at least 1 x 10 is detected in the reactor outlet gas or recycle gas -5 The amount of chloride in the feed is then adjusted to a value sufficient to produce ethylene oxide with substantially optimal selectivity.
For the start-up process of ethylene epoxidation process CN 101711239B provides a means for achieving a controlled start-up temperature of the epoxidation process which is higher than the highest reactor temperature achievable by the use of an external heat source, the temperature range being about 240-290 ℃. The process utilizes the internal heat of reaction in the reactor to bring the bed temperature and the reactor temperature to a temperature suitable for adjusting the high selectivity catalyst.
CN 102666514B describes a process for starting up the epoxidation of ethylene. The method comprises the following steps: the feed gas composed of ethylene and oxygen is introduced in the presence of an epoxidation catalyst at a temperature in the range of 180 ℃ to 210 ℃. And adding about 0.05 to 2ppm moderator to the feed gas; the first temperature is raised to a second temperature of 240 ℃ to 250 ℃ over about 12 hours to 60 hours and maintained for about 50 hours to 150 hours.
CN 102666515B provides a method for starting up 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 point, a sufficient concentration of the modifier is added such that the amount of modifier adsorbed on the catalyst after the second temperature is reached is about 10-50g/m 3 A catalyst; continuing to maintain the second temperature for a period of about 50-350 hours while adding 0.5% -25% carbon dioxide to the feed gas; the second temperature is reduced to a third temperature while the concentration of the regulator is increased.
CN 103261178A describes a method for starting upA method for preparing an efficient alkylene oxide catalyst. The process comprises reacting a feed gas comprising olefins, oxygen and at least one organic chloride over a high efficiency silver catalyst such that no more than 0.03kT ethylene oxide/m after the first start of the reactor 3 The reaction temperature is 215 ℃ to 240 ℃ and the molar ratio of oxygen to ethylene in the feed gas is at least 0.2 during the catalyst aging period of the catalyst.
The high-selectivity series silver catalyst needs a certain period of time for domestication in the initial stage of starting 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 is designed at the initial stage of start-up according to the characteristics of the high-selectivity series silver catalysts. On the basis of stable operation, the activity of the catalyst is effectively controlled, and the selectivity of the catalyst is quickly raised. By optimizing the initial process conditions, a foundation is laid for long-term stable and efficient operation of the catalyst. Therefore, it is very significant to develop a start-up method that can protect the high-selectivity silver catalyst and optimize the catalyst operating conditions.
In the ethylene epoxidation reaction process, flexible regulation of temperature is an important regulation means, but for many small-scale enterprises or limited by specific reaction requirements, the regulation of the temperature of the reactor cannot be realized, so that the starting can only be carried out at constant temperature, and the technical problem is solved for smooth starting of the ethylene epoxidation process by adopting the high-selectivity silver catalyst. Therefore, there is a need to develop a start-up method for high selectivity silver catalysts, and at constant temperature, to meet the actual industrial needs of these enterprises.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an ethylene epoxidation constant-temperature driving method.
Specifically, the invention provides an ethylene epoxidation constant-temperature driving method, which comprises the following steps:
at a constant reaction temperature of 200-230 ℃, in the presence of a high-selectivity silver catalyst for ethylene epoxidation, introducing a feed gas containing ethylene, oxygen and a regulator, and starting the ethylene epoxidation to generate ethylene oxide;
the whole reaction starting process comprises three stages, wherein the first stage is 0-T 1 Time period, the second stage is T 1 -T 2 Time period, the third stage is T 2 To the end of the reaction initiation process, wherein T 1 For 12-24 hours, T 2 72 to 96 hours; the amount of the regulator added ranges from 0.1ppm to 10ppm throughout the reaction initiation.
The 0 time point of the first stage is the time point of starting the reaction, T 1 、T 2 The time point is counted from the time point at which the start of the reaction is started.
The constant-temperature driving of the invention means that the temperature is always constant at a certain constant value within a temperature range of 200 ℃ to 230 ℃ in the whole driving process.
The concept of a high selectivity silver catalyst referred to herein is well known to those skilled in the art and refers to a silver catalyst having a selectivity of 85 to 88%. Because the high-selection series silver catalyst has high initial activity, has the characteristics of a certain time of domestication period and the like, the driving process needs to be matched with the characteristics thereof. In addition, under the requirement of constant-temperature driving, the invention realizes smooth driving by adjusting the addition amount of oxygen, ethylene and regulator in the whole driving starting process so as to achieve the optimal process condition.
According to the process of the invention, preferably the regulator is added in the first stage in an amount C T1 Higher than the addition amount C of the second stage T2 More preferably, C T2 And C T1 Difference DeltaC of (C) T 0.1-1ppm; preferably, the modifier is added in the second and third stages in an amount such that the catalyst selectivity S remains 80% or more. Since the temperature is required to be constant, in the process of gradually increasing the inlet oxygen concentration, the regulator is required to maintain the stability of starting, and when the selectivity S of the catalyst is lower than 80%, the amount of the regulator is properly increased until the selectivity S is more than or equal to 80%, so that the inlet oxygen concentration can be continuously increased gradually.
The selectivity S is calculated in the present invention by methods known in the art to continuously determine the reactor inlet and outlet gas composition on-line. After the measurement result is subjected to volume shrinkage correction, the selectivity (S) is calculated according to the following formula:
where ΔEO is the difference in concentration of ethylene oxide in the reactor outlet gas and inlet gas, ΔCO 2 Is the concentration difference between the carbon dioxide in the outlet gas and the inlet gas of the reactor.
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 regulator is selected from at least one of methyl chloride, ethyl chloride and vinyl chloride. The chloromethane is, for example, chloromethane, dichloromethane, the chloroethane is, for example, chloroethane, dichloroethane, and the chloroethylene is, for example, chloroethylene, dichloroethylene.
According to the process of the invention, the amount of ethylene used is adjusted according to the reaction stage. Preferably, in the first stage and the second stage, the ethylene content in the feed gas is maintained between 1mol% and 15mol%, based on the total molar amount of feed gas; in a third stage, the ethylene content in the feed gas is gradually increased to a set value; the setpoint is preferably 28mol% to 30mol%, based on the total molar amount of feed gas.
According to the method of the invention, the amount of oxygen used is adjusted according to the reaction stage. Preferably, in the first stage, the oxygen content in the feed gas is stepped up from 0 to C O1 Further raise to C in the second stage O2 Further up to or maintained at the set point in the third stage, C O1 1mol% to 1.5mol%, C O2 From 5mol% to 7.5mol%, based on the total molar amount of feed gas.
In the whole reaction starting process, firstly controlling the inlet oxygen concentration to be not more than 1.5mol percent, stabilizing the ethylene concentration to be 15mol percent, and properly increasing the addition amount of EDC until the oxygen concentration at the outlet of the reactor is reached; when the selectivity S of the catalyst is lower than 80%, the operation is optimized, and the inlet oxygen concentration cannot be continuously increased gradually until the selectivity S is more than or equal to 80%. The oxygen concentration increasing rate is 0.2 to 0.8mol% per 4 hours. Gradually up to a set point (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, with the rate of increase being increased by 1-2mol% every 4 hours, to the set point (e.g., 28 mol%).
According to the invention, it is preferred that the concentration of carbon dioxide is kept less than 3mol% throughout the start-up of the reaction, and that the fluctuation range in the second stage and the third stage is not more than 1mol% based on the total molar amount of the feed gas. In the initial stage, the concentration of the carbon dioxide is continuously accumulated along with the progress of the reaction, and when the reaction is continued, the concentration of the carbon dioxide is continuously increased, and the carbon dioxide can be discharged or increased as required, so that the concentration is kept within the range.
According to the present invention, it is preferable that the holding selectivity is 85% -90% in the second stage and the third stage (during the holding step).
In the process of the invention, the total duration of the entire reaction start-up procedure may be 120 to 144 hours.
The ethylene epoxidation constant temperature start-up process of the present invention is applicable to a variety of high selectivity silver catalysts, which typically comprise an alpha-alumina support and supported thereon the following components: silver, alkali metal promoters, alkaline earth metal promoters, rhenium promoters, and optionally, rhenium co-promoters.
Further, the silver is contained in an amount of 1 to 35wt%, preferably 15 to 30wt%, based on the total weight of the catalyst.
In the high selectivity silver catalyst employed 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 nitrate, sulfate or hydroxide of these alkali metals, preferably cesium sulfate and/or cesium nitrate. The content of alkali metal in the silver catalyst, calculated as alkali metal element, is 5 to 2000ppm, preferably 10 to 1500ppm, based on the total weight of the catalyst.
In the high selectivity silver catalyst employed 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 alkaline earth metal content of the silver catalyst is 5 to 2200ppm, preferably 10 to 1500ppm, in terms of alkaline earth metal element based on the total weight of the catalyst.
In the high selectivity silver catalyst employed in the present invention, the rhenium promoter may be at least one of a rhenium oxide, a perrhenic acid, and a perrhenate, preferably ammonium perrhenate and/or cesium perrhenate. The content of rhenium promoter in the silver catalyst is 5 to 1500ppm, preferably 10 to 1000ppm, based on the total weight of the catalyst, calculated as rhenium element.
In the high selectivity silver catalyst employed in the present invention, the co-promoter of the rhenium promoter optionally used may be a compound of any transition metal 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 0 to 1000ppm, preferably 10 to 500ppm, based on the total weight of the catalyst.
The high selectivity silver catalyst can be prepared by methods conventional in the art. For example, the alumina support is impregnated with an impregnating solution. The alumina support is preferably a porous alpha-alumina support, further preferably having the following characteristics: the content of alpha-alumina is more than or equal to 90wt percent, and the specific surface area is 0.8-3.0m 2 Per gram, pore volume of 0.3-0.8ml/g, water absorption of 30-70% and crushing strength of 50-200N/granule.
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 measuring instrument, a carrier sample is selected, and the average value is obtained after the radial crushing strength is measured.
The alpha-alumina support used in the present invention may also be prepared by methods conventional in the art.
The method for starting the high-selectivity silver catalyst in the process of preparing ethylene oxide by epoxidation of ethylene, provided by the invention, is characterized in that the device always keeps constant temperature operation within the temperature range of about 200 ℃ to about 230 ℃ in the process of starting the catalyst. The method of constant temperature start-up is adopted, so that the temperature operation requirement in the reaction start-up process is greatly reduced, and the method of constant temperature start-up at a lower temperature can fully utilize the reaction heat generated by the reaction, can effectively avoid the problem of temperature runaway caused by the over-high initial activity of the high-selectivity catalyst, and can achieve two purposes. Meanwhile, under the condition of no rapid load lifting requirement, the reaction temperature is kept constant, and the reaction is more favorably and mildly carried out. The continuous and stable temperature environment is beneficial to the domestication of the catalyst in the initial stage of the reaction.
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 continuously measured on-line for the gas composition at the inlet and outlet of the reactor by detection means such as mass spectrometry. After the measurement result is subjected to volume shrinkage correction, the selectivity (S) is calculated according to the following formula:
where ΔEO is the difference in concentration of ethylene oxide in the reactor outlet gas and inlet gas, ΔCO 2 Is the concentration difference between the carbon dioxide in the outlet gas and the inlet gas of the reactor.
Preparation example 1
This preparation example is used to illustrate the high selectivity silver catalyst used in the examples of the present invention and the preparation method thereof.
(1) Preparation of high-selectivity silver catalyst carrier
alpha-Al trihydrate of 50-200 meshes 2 O 3 450g and 200-500 mesh pseudo-monohydrate Al 2 O 3 100g of the mixture is put into a mixer and mixed uniformly. Then transferring 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 into the kneader, and kneading into paste capable of extrusion molding. Extruding to obtain five-hole column with outer diameter of 8.0mm, length of 6.0mm and inner diameter of 1.0mm, and drying at 60-120deg.C for 3 hr to reduce free water content below 10wt% to obtain green compact. Then placing the green body into an electric furnace, raising the temperature from room temperature to 1410-1450 ℃ for 30 hours, and keeping the temperature for 2 hours to obtain white porous alpha-Al 2 O 3 Carrier sample.
The obtained porous alpha-Al 2 O 3 The carrier is characterized as follows: alpha-A1 2 O 3 The content is more than 90%, and the crushing strength is 20-200N/granule; the specific surface is 0.2-3.0m 2 /g; the water absorption is not lower than 30%; the pore volume is 0.30-0.85ml/g.
(2) Preparation of high selectivity silver catalyst
Firstly, reacting an aqueous solution of silver nitrate with ammonium oxalate or an aqueous solution of oxalic acid to precipitate silver oxalate, filtering, washing with deionized water until nitrate ions are absent, then dissolving silver oxalate into a mixed solution of ethylenediamine and ethanolamine, and adding an auxiliary agent and urea to prepare a silver ammonia impregnating solution. The alumina carrier was then impregnated with the resulting impregnation solution, drained, and held in an air stream at a temperature range of 400 ℃ for 10 minutes to effect thermal decomposition.
The silver catalyst produced contained 28% silver, 100ppm alkali metal, 100ppm alkaline earth metal and 600ppm rhenium based on the total weight thereof.
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 injection: before oxygen addition, the reactor was purged with nitrogen to provide an oxygen content of <0.5mol% in the gas leaving the reactor. After the oxygen content of the displacement gas leaving the reactor was <0.5mol%, nitrogen was introduced to raise the reactor pressure to 1.8-1.9 MPa. And the catalyst bed temperature was maintained at 200 c using the apparatus heating device.
2. Oxygen preparation: the temperature of the device is kept at 218 ℃, the system pressure is about 2.1MPa and C 2 H 4 The concentration was 15.0mol% and remained stable.
3. The oxygen dosing reaction was performed under the specific conditions shown in the pilot plant start-up schedule (Table 1):
the first stage: the inhibitor EDC was added to the recycle gas at substantially steady temperature, pressure and ethylene concentration, and oxygen was added after 10 minutes. The oxygen feeding speed is slow, so that the inlet gas O gradually 2 The concentration reaches between 0.5 and 1.0mol percent and is maintained for 1 to 2 hours. The oxygen concentration was then increased and the inhibitor addition was adjusted to allow oxygen to appear at the reactor outlet.
And a second stage: the ethylene concentration is kept unchanged, the oxygen concentration is gradually increased, and when the selectivity S of the catalyst is lower than 80%, the content of the inhibitor is regulated until the selectivity S is more than or equal to 80%, and then the inlet oxygen concentration is gradually increased to 7.5mol%. The oxygen concentration increasing rate was increased by 0.5mol% every 4 hours.
And a third stage: when the system oxygen concentration reached 7.5%, the ethylene concentration was gradually increased to 28mol% at the set point under steady reaction conditions, at a rate of 1.5mol% per 4 hours, thereby increasing the outlet EO concentration to the set point (1% -3%).
Table 1 reference timetable for start-up operation of pilot plant
Example 2
A certain plant uses a YS series of high selectivity silver catalysts. 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%; the temperature of the reactor is increased to 218 ℃ and the reactor has feeding and starting conditions.
Firstly, ethylene is added to 15mol% in a device system; the regulator dichloroethane (EDC) was added to the system at a rate of 1500g/h 10 minutes before the oxygen addition to the apparatus. After the oxygen adding preparation work is finished, a small distributor is opened, the minimum oxygen adding amount is used for adding oxygen into the system, and the reaction is successful once after oxygen adding. The catalyst activity is higher in the initial reaction period of 0-24 hours, and the catalyst activity can be effectively controlled by adding a large amount of EDC, and the total chlorine of the system is about 5.0ppm. Optimizing the system within 24-72 hours, gradually reducing the addition amount of the regulator, and controlling the total chlorine in the system to be about 4.0ppm; gradually increasing the load of the device, increasing the oxygen adding amount, gradually increasing the oxygen concentration to about 5mol%, and gradually increasing the selectivity of the catalyst at the moment, wherein the average selectivity exceeds 83%. After 72-120 hours, the device switches the large distributor to throw oxygen and switches the oxygen into methane to be stable along with the lifting of the load. Increasing the oxygen concentration of the system load to 7.5%, and increasing the ethylene load to 28%; the total chlorine of the system is controlled at about 2.0-3.0ppm. After 120 hours the catalyst was acclimatized, the oxygen and ethylene concentrations were maintained, the drum temperature was maintained constant, and the chloride addition was continued to be optimized to about 2.5ppm.
Finally, the catalyst reaction temperature was constantly controlled at about 218℃and total chlorine was maintained at about 2.5ppm. Ethylene feed 3.6 tons/hr and oxygen feed 3.85 tons/hr. Ethylene concentration 27.61%, oxygen concentration 8.35%, carbon dioxide concentration 1.82%, and outlet EO 2.23%. Average selectivity was 85.2% and feed selectivity 86.47%.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.
Claims (12)
1. A constant temperature start-up method for ethylene epoxidation, comprising:
at a constant reaction temperature of 200-230 ℃, in the presence of a high-selectivity silver catalyst for ethylene epoxidation, introducing a feed gas containing ethylene, oxygen and a regulator, and starting the ethylene epoxidation to generate ethylene oxide;
the whole reaction starting process comprises three stages, wherein the first stage is 0-T 1 Time period, the second stage is T 1 -T 2 Time period, the third stage is T 2 To the end of the reaction initiation process, wherein T 1 For 12-24 hours, T 2 72 to 96 hours; the addition amount of the regulator ranges from 0.1ppm to 10ppm in the whole reaction starting process;
the addition amount C of the regulator in the first stage T1 Higher than the addition amount C of the second stage T2 The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the regulator in the second stage and the third stage ensures that the catalyst selectivity S is maintained to be more than or equal to 80 percent;
in the first stage and the second stage, the ethylene content in the feed gas is maintained between 1mol% and 15mol%, based on the total molar amount of feed gas; in a third stage, the ethylene content in the feed gas is gradually increased to a set value;
in the first stage, the oxygen content in the feed gas is gradually increased from 0 to C O1 Further raise to C in the second stage O2 Further up to or maintained at the set point in the third stage, C O1 1mol% to 1.5mol%, C O2 5mol% to 7.5mol%, based on the total molar amount of feed gas;
the concentration of carbon dioxide is maintained at less than 3 mole% throughout the start-up of the reaction, and the amplitude of the fluctuations in the second and third stages is no more than 1 mole% based on the total molar amount of feed gas.
2. The ethylene epoxidation constant temperature driving method of claim 1, wherein C T2 And C T1 Difference DeltaC of (C) T 0.1-1ppm.
3. The ethylene epoxidation process of claim 1 wherein the modifier is selected from the group consisting of organohalocarbons.
4. A process for the epoxidation of ethylene in a constant temperature drive as recited in claim 3 wherein the modifier is selected from at least one of methyl chloride, ethyl chloride and vinyl chloride.
5. The ethylene epoxidation constant temperature driving method of claim 1, wherein the setpoint is 28mol% to 30mol%, based on the total molar amount of the feed gas.
6. The ethylene epoxidation constant temperature driving method according to claim 1, wherein the content elevation rate of ethylene in the third stage is increased by 1-2mol% every 4 hours.
7. The ethylene epoxidation constant temperature driving method according to claim 1, wherein the oxygen content increasing speed is increased by 0.2 to 0.8mol% every 4 hours.
8. The ethylene epoxidation process of claim 1 wherein the selectivity is maintained between 85% and 90% in the second stage and the third stage.
9. The ethylene epoxidation constant temperature driving method of claim 1, wherein the total duration of the entire reaction initiation process is 120 to 144 hours.
10. The ethylene epoxidation process of any of claims 1-9 wherein the high selectivity silver catalyst comprises an a-alumina support and supported thereon the following components: silver, alkali metal promoters, alkaline earth metal promoters, rhenium promoters, and optionally, rhenium co-promoters.
11. The ethylene epoxidation constant temperature start-up process of claim 10, wherein the silver is present in an amount of from 1 to 35wt% based on the total weight of the catalyst; the content of the alkali metal is 5-2000ppm; the alkaline earth metal content is 5-2200ppm; the content of the rhenium auxiliary agent is 5-1500ppm; the content of the synergistic auxiliary element of rhenium is 0-1000ppm.
12. The ethylene epoxidation constant temperature drive of claim 11, wherein the silver is present in an amount of from 15 to 30 percent by weight, based on the total weight of the catalyst; the content of the alkali metal is 10-1500ppm; the alkaline earth metal content is 10-1500ppm; the content of the rhenium auxiliary agent is 10-1000ppm; the content of the synergistic auxiliary element of rhenium is 10-500ppm.
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