CN113912498A - Method and device for safely preparing methyl nitrite in oxidation esterification reactor and application of methyl nitrite - Google Patents
Method and device for safely preparing methyl nitrite in oxidation esterification reactor and application of methyl nitrite Download PDFInfo
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- 230000003647 oxidation Effects 0.000 title claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 63
- 230000032050 esterification Effects 0.000 title claims abstract description 60
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 447
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 88
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000001301 oxygen Substances 0.000 claims abstract description 83
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 83
- 238000006709 oxidative esterification reaction Methods 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 42
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 239000011261 inert gas Substances 0.000 claims description 15
- 238000011049 filling Methods 0.000 claims description 12
- 238000012544 monitoring process Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004880 explosion Methods 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
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- 238000004519 manufacturing process Methods 0.000 description 24
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- 238000005516 engineering process Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000005273 aeration Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
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- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of ethylene glycol synthesis, and discloses a method for safely preparing methyl nitrite in an oxidative esterification reactor, which comprises the following steps: introducing fresh methanol, nitric oxide and oxygen into an oxidative esterification reactor to carry out oxidative esterification reaction at a set temperature T and a set pressure P, wherein unreacted gas phase is used for recovering cold methanol, and the recovered cold methanol is refluxed into the oxidative esterification reactor to participate in the oxidative esterification reaction. The method and the oxidation esterification reactor provided by the invention can effectively prevent burning explosion in the preparation process of methyl nitrite, ensure the use of the methyl nitrite in a coupling section and realize the safe industrial production of preparing ethylene glycol from synthesis gas.
Description
Technical Field
The invention relates to the field of ethylene glycol preparation, and in particular relates to a method and a device for safely preparing methyl nitrite in an oxidative esterification reactor and application of the methyl nitrite.
Background
Ethylene Glycol (EG) is an important petrochemical basic organic raw material and has wide application. The global ethylene glycol production capacity is about 3747 ten thousand tons in 2016, the consumption is 2614.5 ten thousand tons, and 85 percent of ethylene glycol is used in the polyester industry. At present, the industrial production of large-scale ethylene glycol at home and abroad mainly adopts a process route of a direct ethylene oxide hydration method, namely, ethylene is synthesized by a petroleum route, then ethylene oxide is oxidized to produce ethylene oxide, and finally EG is obtained by non-catalytic hydration reaction of ethylene oxide. The production technology is basically monopolized by three companies, Shell, Halcon-SD and UCC. The economic benefit of the production process is limited by the price of petroleum, and the fluctuation is large.
In recent years, with the large demand for ethylene glycol for polyester fibers, polyester plastics, antifreeze, and the like, research and development work on new synthetic techniques for ethylene glycol has been focused. The production technology for preparing ethylene glycol by using an ethylene oxide catalytic hydration method is successively developed by Shell company, UCC company, Moscout Mendeleev chemical industry institute and the like; the companies, Halcon-SD, UCC, Dow chemical, Japanese catalyst chemical and Mitsubishi chemical, have developed ethylene glycol production technologies by the ethylene carbonate process. In addition, due to the shortage of petroleum resources in the world and the relative abundance of natural gas resources, research and development work for a new process for preparing ethylene glycol from synthesis gas is also being carried out by companies such as UCC in the united states and prosperous product of the japanese ministry of japan. At present, petroleum resources are increasingly tense, and the price is in high-order operation for a long time, finding an economic and reasonable ethylene glycol synthesis route has become a research hotspot. The process for synthesizing the ethylene glycol by taking the synthesis gas as the main raw material is emphasized by the advantages of wide and cheap raw material sources, high technical economy and the like.
At present, a new technology for preparing ethylene glycol is developed by using synthesis gas resources as production raw materials in China, and the technological process of the technology comprises synthesis gas separation, methyl nitrite coupling, oxidation esterification technology, oxalate hydrogenation and the like.
However, the process for preparing ethylene glycol from synthesis gas involves unstable intermediate methyl nitrite and lacks an accurate method for preventing burning explosion of methyl nitrite, so that safe use of methyl nitrite in a coupling section cannot be ensured. At present, no systematic research on the danger and safety control scheme in the aspect is available in China, so that the danger of the industrial device for preparing the glycol from the synthesis gas cannot be effectively controlled, and if the problem cannot be timely and effectively solved, the safe operation of the device for preparing the glycol from the synthesis gas is necessarily restricted.
Disclosure of Invention
The invention aims to overcome the problem that the dangerous characteristic of an oxidation esterification reactor in the process of preparing ethylene glycol by using synthesis gas in the prior art is lack of safety guarantee, and provides a method for safely preparing methyl nitrite in the oxidation esterification reactor.
In order to achieve the above object, one aspect of the present invention provides a method for safely preparing methyl nitrite in an oxidative esterification reactor, the method comprising: introducing fresh methanol, nitric oxide and oxygen into an oxidation esterification reactor to carry out oxidation esterification reaction at a set temperature T and a set pressure P, wherein unreacted gas phase is used for recovering the methanol, and recovered cold methanol is refluxed to the oxidation esterification reactor to participate in the oxidation esterification reaction, and the method is characterized by comprising the steps of measuring the temperature and/or the pressure in the oxidation esterification reactor regularly or irregularly, and controlling the temperature and/or the pressure in the oxidation esterification reactor according to the measurement result by adopting the following hierarchical control mode so that the temperature in the oxidation esterification reactor is maintained at T and/or the pressure in the oxidation esterification reactor is maintained at P:
increasing the amount of recovered cold methanol reflux when the temperature is T1 or the pressure is P1;
when the temperature is T2 or the pressure is P2, the reflux amount of the recovered cold methanol is increased and the reaction is stopped;
wherein T is more than T1 and less than T2, and T2-T is more than or equal to 30 ℃;
p is more than P1 and more than P2, and P2-P is more than or equal to 0.17 MPa.
In a second aspect, the present invention provides an apparatus for producing ethylene glycol from synthesis gas, the apparatus comprising an oxidative esterification reactor in which the temperature and pressure are controlled by the above method.
In a third aspect, the invention provides the use of the above method and apparatus in a process for the preparation of ethylene glycol from synthesis gas.
Through the technical scheme, in the process for preparing the ethylene glycol by utilizing the synthesis gas, burning explosion of the methyl nitrite can be effectively prevented, so that safe use of the methyl nitrite in a coupling section is ensured, and safe industrial production of preparing the ethylene glycol by utilizing the synthesis gas is realized.
Drawings
FIG. 1 is a schematic view of an oxidative esterification reactor apparatus provided by the present invention.
Description of the reference numerals
1 is a liquid distributor, 2 is a gas distributor, and 3 is a filler.
Detailed Description
It should be understood that the following detailed description is only intended to illustrate and describe the present invention, and is not intended to limit the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for safely preparing methyl nitrite in an oxidative esterification reactor, the method comprising: introducing fresh methanol, nitric oxide and oxygen into an oxidative esterification reactor to carry out oxidative esterification at a set temperature T and a set pressure P, wherein unreacted gas phase is used for recovering methanol, and recovered cold methanol is refluxed into the oxidative esterification reactor to participate in the oxidative esterification reaction, and the method is characterized by comprising the steps of measuring the temperature and/or the pressure in the oxidative esterification reactor regularly or irregularly, and controlling the temperature and/or the pressure in the oxidative esterification reactor according to the measurement result by adopting the following hierarchical control mode, so that the temperature in the oxidative esterification reactor is maintained at T and/or the pressure in the oxidative esterification reactor is maintained at P (normal production level):
increasing the amount of recovered cold methanol reflux when the temperature is T1 or the pressure is P1;
when the temperature is T2 or the pressure is P2, the reflux amount of the recovered cold methanol is increased and the reaction is stopped;
wherein T is more than T1 and less than T2, and T2-T is more than or equal to 30 ℃;
p is more than P1 and more than P2, and P2-P is more than or equal to 0.17 MPa.
According to the invention, the method for preparing methyl nitrite in the oxidation esterification reactor comprises the following steps: introducing methanol, nitric oxide and oxygen into an oxidation esterification reactor to perform oxidation esterification reaction at a set temperature T and a set pressure P, wherein unreacted gas phase is used for recovering cold methanol, and the recovered cold methanol is refluxed to the oxidation esterification reactor to participate in the oxidation esterification reaction. Methods for recovering cold methanol from the unreacted gas phase include condensation, fractionation, adsorption, and the like. The temperature of the recovered cold methanol is generally-15-30 ℃.
According to a preferred embodiment of the present invention, wherein the oxidative esterification reaction comprises: in the oxidative esterification reactor, methanol, nitric oxide and oxygen are reacted to produce methyl nitrite by:
2CH3OH+2NO+1/2O2→2CH3ONO+H2O
preferably, the conditions of the oxidative esterification reaction include: the set temperature T is 20-55 deg.C, and the set pressure P is 0.1-0.28 MPa.
More preferably, the conditions of the oxidative esterification reaction include: the set temperature T is 25-40 deg.C, and the set pressure P is 0.1-0.2 MPa.
According to a preferred embodiment of the present invention, wherein the molar ratio of fresh methanol, nitric oxide and oxygen introduced into the oxidative esterification reactor is 200: 1-40: 1-10, preferably 100: 3-40: 2-10, the reflux quantity (the reflux quantity when the temperature and the pressure are respectively T and P) of the recovered cold methanol is 0.25-0.98 of the total methanol feed, and the temperature of the recovered cold methanol is-15-30 ℃.
According to the invention, the reaction can be stopped in a conventional manner, preferably by cutting off the oxygen feed and replacing it with an inert gas.
According to the invention, wherein said means for measuring the temperature and/or pressure in the oxidative esterification reactor, either periodically or not, comprise: the temperature and/or pressure in the oxidation esterification reactor are monitored by measuring once every 0.5-3min or measuring 1-10 times irregularly within 5min in an on-line detection mode.
According to the invention, the method adopts a layered control mode to control the temperature and/or the pressure in the oxidation esterification reactor. The hierarchical control is realized by monitoring the temperature and/or the pressure in the oxidation esterification reactor, dividing the temperature and/or the pressure into different levels and adopting different control measures aiming at the temperature and/or the pressure of the different levels.
According to a preferred embodiment of the present invention, wherein, when the temperature is T1, the amount of recovered cold methanol reflux is increased while monitoring and adjusting the fresh methanol flow rate; or
When the temperature is T2, increasing the reflux quantity of the recovered cold methanol, cutting off the oxygen feeding and filling inactive gas for replacement, and stopping the reaction; or
When the pressure is P1, the return flow of recovered cold methanol is increased while the flow of fresh methanol is monitored and adjusted; or
When the pressure is P2, the amount of recovered cold methanol reflux is increased while the oxygen feed is cut off and replaced with inert gas, and the reaction is stopped.
Preferably, the fresh methanol flow is monitored by a flange turbine flowmeter in real time.
According to a preferred embodiment of the invention, the reflux of the recovered cold methanol is increased to 1.6 to 2.5 times the original reflux at 55 ℃ < T1 ≦ 65 ℃. Meanwhile, monitoring the flow of fresh methanol, and increasing the flow of the fresh methanol to 90-120% of the original flow when the flow of the fresh methanol is 70-80% of the original flow; when the fresh methanol flow is lower than 70% of the original flow, the oxygen feed is cut off.
According to a preferred embodiment of the present invention, when the temperature in the oxidative esterification reactor is restored from T1 to the set temperature T, the recovered cold methanol reflux amount, fresh methanol flow rate and oxygen flow rate are restored to normal production condition levels.
According to a preferred embodiment of the invention, wherein 65 ℃ T2 ≦ 75 ℃, the reflux of recovered cold methanol is increased to 2.2 to 3.6 times the original reflux. At the same time, the oxygen feed is cut off, the reaction is stopped, and inert gas is filled for replacement. The aeration amount of the inert gas in the method of the present invention is not particularly required, so long as the oxygen in the oxidative esterification reactor can be substantially replaced, thereby terminating the reaction. In addition, the replacement of oxygen can also play a role in preventing burning explosion of methyl nitrite, so that the safety of the method provided by the invention is further improved.
According to a preferred embodiment of the invention, wherein T2 > 75 ℃, the reflux of recovered cold methanol is increased to 3.2-5.6 times the original reflux. At the same time, the oxygen feed is cut off, the reaction is stopped, and inert gas is filled for replacement. The aeration amount of the inert gas in the method of the present invention is not particularly required, so long as the oxygen in the oxidative esterification reactor can be substantially replaced, thereby terminating the reaction. In addition, the replacement of oxygen can also play a role in preventing burning explosion of methyl nitrite, so that the safety of the method provided by the invention is further improved.
According to a preferred embodiment of the present invention, when the temperature in the oxidative esterification reactor is restored from T2 to 45-55 ℃, the charging of the inert gas is stopped. When the temperature in the oxidative esterification reactor is restored from T2 to 30-45 ℃, the oxygen feed is restarted. When the temperature in the oxidation esterification reactor is recovered to the set temperature T from T2, the oxygen input amount and the recovered cold methanol reflux amount are recovered to the normal production level.
According to the preferred embodiment of the invention, wherein, the P1 is more than 0.28MPa and less than or equal to 0.35MPa, the return flow of the recovered cold methanol is increased to 1.5-2 times of the original return flow, the flow of the fresh methanol is monitored, when the flow of the fresh methanol is 70-80% of the original flow, the low-flow alarm of the methanol is triggered, and the flow of the methanol is increased to 90-120% of the original flow; when the fresh methanol flow is lower than 70% of the original flow, the feed of the raw material oxygen is cut off. The aeration amount of the inert gas in the method of the present invention is not particularly required, so long as the oxygen in the oxidative esterification reactor can be substantially replaced, thereby terminating the reaction. In addition, the replacement of oxygen can also play a role in preventing burning explosion of methyl nitrite, so that the safety of the method provided by the invention is further improved.
According to a preferred embodiment of the present invention, when the pressure in the oxidative esterification reactor is restored from P1 to the set pressure P, the recovered cold methanol reflux amount, fresh methanol flow rate and oxygen flow rate are restored to normal production condition levels.
According to a preferred embodiment of the invention, wherein 0.35MPa < P2 ≦ 0.45MPa, the reflux of recovered cold methanol is increased to 2-3.2 times the original reflux. At the same time, the oxygen feed is cut off, the reaction is stopped, and inert gas is filled for replacement.
According to a preferred embodiment of the invention, where P2 > 0.45MPa, the reflux of recovered cold methanol is increased to 3-5.3 times the original reflux, while the oxygen feed is cut off and the reaction is stopped. The aeration amount of the inert gas in the method of the present invention is not particularly required, so long as the oxygen in the oxidative esterification reactor can be substantially replaced, thereby terminating the reaction. In addition, the replacement of oxygen can also play a role in preventing burning explosion of methyl nitrite, so that the safety of the method provided by the invention is further improved.
According to a preferred embodiment of the present invention, when the pressure in the oxidative esterification reactor is restored to 0.3 to 0.4MPa, the filling of the inert gas is stopped. When the pressure in the oxidative esterification reactor is restored to 0.2-0.3MPa, the oxygen feed is restarted. When the pressure in the oxidation esterification reactor is recovered to the set pressure P, the oxygen introduction amount and the recovered cold methanol reflux amount are recovered to the normal production level
According to a preferred embodiment of the present invention, the inert gas in the above method may be any gas that does not participate in the oxidative esterification reaction.
Preferably, the inert gas comprises: at least one of nitrogen, helium, argon, and carbon dioxide.
More preferably, the inert gas is nitrogen for reasons of production cost and convenience of gas source.
According to a preferred embodiment of the present invention, when both the temperature and the pressure in the oxidative esterification reactor are out of the range of the set temperature T and the set pressure P, the temperature and the pressure in the oxidative esterification reactor are controlled in a control manner in which the parameters of higher severity of the out-going are used.
Specifically, when the temperature in the oxidation esterification reactor is measured to be T1 and the pressure is measured to be P2, the reaction conditions in the oxidation esterification reactor are controlled in a control mode with the pressure being P2.
Specifically, when the temperature in the oxidation esterification reactor is measured to be T2 and the pressure is measured to be P1, the reaction conditions in the oxidation esterification reactor are controlled according to the control mode of the temperature T2.
According to a preferred embodiment of the present invention, for the purpose of preventing oxygen from being unevenly distributed and aggregated in a small range, the method further comprises dividing the oxygen supplied to the oxidative esterification reactor into 3-20 oxygen streams, which enter different positions in the reactor respectively to perform oxidative esterification with methanol and recycle gas. Wherein the circulating gas is a mixed gas containing nitric oxide and methanol. The aim of this operation is to reduce side reactions, increase the yield, and reduce the risk of high temperature and high pressure in the reactor. Therefore, the skilled person can select the fraction of oxygen to be divided according to the actual situation.
Preferably, the oxygen supplied to the oxidative esterification reactor is divided into 6 to 10 streams which enter different positions in the reactor respectively to perform oxidative esterification with methanol and recycle gas in view of reducing cost, improving production efficiency, preventing oxygen from being unevenly distributed, gathering in a small range and improving conversion rate.
More preferably, in view of cost reduction, production efficiency improvement and prevention of oxygen maldistribution, aggregation in a small range and conversion improvement, oxygen feed ports are provided at positions 1/(n +1), 2/(n +1), 3/(n +1), 4/(n +1) … n/(n +1) in the longitudinal height direction of the oxidative esterification reactor, respectively, and the feed amount of each oxygen stream is different, and the feed ratio of oxygen from the inlet to the outlet is: n: n-1: n-2: …: 1. Where n is the number of oxygen feed strands.
Further preferably, oxygen feed inlets are arranged at the positions of 1/(n +2), 2/(n +2), 3/(n +2), 4/(n +2) … (n +1)/(n +2) in the longitudinal height direction of the oxidative esterification reactor, and the feed amount of each oxygen is respectively different, and the ratio from the inlet to the outlet is: n: n-1: n-2: …: 1. Where n is the number of oxygen feed strands.
The invention provides a device for preparing ethylene glycol from synthesis gas in a second aspect. The apparatus comprises an oxidative esterification reactor with temperature and/or pressure control via the above-described layered control scheme.
According to a preferred embodiment of the present invention, wherein the apparatus further comprises a safety valve disposed within the oxidative esterification reactor.
According to a preferred embodiment of the present invention, wherein the safety valve is provided for the purpose of further preventing the occurrence of a runaway reaction of high temperature and high pressure in the reactor. Therefore, any safety valve in the art that achieves the above objectives may be suitable for use with the apparatus provided by the present invention.
Preferably, the safety valve is a safety valve arranged according to the fire conditions specified in American Petroleum institute standard API-520.
In a third aspect, the invention provides the use of the above method and apparatus in a process for the preparation of ethylene glycol from synthesis gas.
In the invention, the synthesis gas refers to at least one of calcium carbide furnace tail gas and coke oven gas, and comprises components such as carbon monoxide.
The present invention will be described in detail below by way of examples. It is to be understood that the following examples are intended only to further illustrate and explain the present invention, and are not intended to limit the present invention.
In the following examples, the oxidative esterification reaction was carried out by using the apparatus shown in FIG. 1 without specific explanation. The filler 3 in the device is alumina spherical filler, the filler amount is above 4/5 of the reactor height, methanol is evenly distributed in the reactor through the liquid distributor 1, and oxygen and nitric oxide are evenly distributed in the reactor through the gas distributor 2. Wherein, the oxygen is divided into 3 strands and respectively enters the oxidation esterification reactor from the 1/4, 2/4 and 3/4 positions in the height direction of the oxidation esterification reactor, and the feeding amount ratio of each oxygen is as follows according to the sequence from the inlet to the outlet: 3:2:1. Fresh methanol, reflux methanol and nitric oxide are respectively arranged in the liquid distributor. Nitrogen was introduced through a line at the inlet point at the top of the reactor. The temperature and pressure in the oxidative esterification reactor were measured every 3min by means of on-line measurement.
In the following examples and comparative examples, the conversion of the reaction raw material was calculated based on the conversion of oxygen.
In the following examples, the "methanol flow rate" refers to a fresh methanol flow rate unless otherwise specified.
Example 1
The reaction conditions of oxidative esterification are that the temperature is 20 ℃, the pressure is 0.1MPa, and the molar ratio of methanol to nitric oxide to oxygen is 100: 10: 5, the reflux quantity of the cold methanol is 105 +/-15 percent of the original flow. While controlling the temperature and/or pressure within the oxidative esterification reactor in the following manner.
When the temperature in the oxidation esterification reactor reaches 48 ℃, the reflux quantity of the cold methanol is increased to 1.9 times of the original reflux quantity. And meanwhile, when the flow of the methanol is lower than 80% of the original flow, generating a methanol low-flow alarm, and increasing the flow of the methanol to 100% of the original flow. When the flow rate of the methanol is lower than 70 percent of the original flow rate, the feed of the raw material oxygen is cut off in an emergency.
When the temperature in the oxidation esterification reactor reaches 60 ℃, the reflux quantity of the cold methanol is increased to 2.9 times of the original reflux quantity. And on the basis of increasing the reflux quantity of the cold methanol, the oxygen feeding is cut off at the same time, and the reaction is stopped. Meanwhile, nitrogen is filled in emergently for replacement.
When the temperature in the oxidation esterification reactor is reduced to 50 ℃, the cold methanol reflux is recovered to the original reflux, the methanol flow is recovered to the original flow, the nitrogen filling is stopped, the oxygen is introduced again, and the original production flow is recovered.
When the pressure in the oxidation esterification reactor reaches 0.32MPa, the reflux quantity of the cold methanol is increased to 1.8 times of the original reflux quantity. Meanwhile, when the flow of the methanol is lower than 80% of the original flow, a methanol low-flow alarm is generated, and the flow of the methanol is increased to 110% of the original flow; and when the flow rate of the methanol is lower than 70 percent of the original flow rate, the feeding of the raw material oxygen is cut off emergently.
When the pressure in the oxidative esterification reactor exceeded 0.39MPa, the cold methanol reflux increased to 2.4 times the original reflux. And on the basis of increasing the reflux quantity of the cold methanol, the oxygen feeding is cut off at the same time, and the reaction is stopped. And filling nitrogen for replacement in an emergency.
And when the pressure in the oxidation esterification reactor is reduced to 0.25MPa, the cold methanol reflux is recovered to the original reflux, the methanol flow is recovered to the original flow, the nitrogen filling is stopped, the oxygen is introduced again, and the original production flow is recovered.
The method is adopted to produce methyl nitrite from synthesis gas, and the operation is stable for 3000 hours in total. At the end of the run, the system will run,the temperature in the oxidation esterification reactor is 40 ℃, the pressure is 0.25MPa, the conversion rate of reaction raw materials is 94 percent, and the consumption of nitrogen is 0.6 ten thousand m3。
During the operation, 2 times of overtemperature and 2 times of overpressure are totally generated in the oxidation esterification reactor. Wherein, overtemperature appears at 1200 th and 2500 th hours after the operation is started, and when the overtemperature condition occurs, the temperature in the reactor is 48 ℃ and 56 ℃ in sequence. Overpressure appears at 1200 th and 2500 th hours after operation is started, and when the overpressure condition occurs, the pressure in the reactor is 0.35MPa and 0.4MPa in sequence.
Example 2
The reaction conditions of oxidative esterification are that the temperature is 35 ℃, the pressure is 0.2MPa, and the molar ratio of methanol to nitric oxide to oxygen is 150: 20: 7, the reflux amount of the cold methanol is more than 90 percent of the original reflux amount. While controlling the temperature and/or pressure within the oxidative esterification reactor in the following manner.
When the temperature in the oxidation esterification reactor reaches 55 ℃, the reflux quantity of the cold methanol is increased to 2.5 times of the original reflux quantity. And meanwhile, when the flow of the methanol is lower than 80% of the original flow, generating a methanol low-flow alarm, and increasing the flow of the methanol to 120% of the original flow. When the flow rate of the methanol is lower than 70 percent of the original flow rate, the feed of the raw material oxygen is cut off in an emergency.
When the temperature in the oxidation esterification reactor reaches 65 ℃, the reflux quantity of the cold methanol is increased to 3.6 times of the original reflux quantity. And on the basis of increasing the reflux quantity of the cold methanol, the oxygen feeding is cut off at the same time, and the reaction is stopped. Meanwhile, nitrogen is filled in emergently for replacement.
When the temperature in the oxidation esterification reactor is reduced to 50 ℃, the cold methanol reflux is recovered to the original reflux, the methanol flow is recovered to the original flow, the nitrogen filling is stopped, the oxygen is introduced again, and the original production flow is recovered.
When the pressure in the oxidation esterification reactor reaches 0.35MPa, the reflux quantity of the cold methanol is increased to 2 times of the original reflux quantity. Meanwhile, when the flow of the methanol is lower than 80% of the original flow, a methanol low-flow alarm is generated, and the flow of the methanol is increased to 120% of the original flow; and when the flow rate of the methanol is lower than 70 percent of the original flow rate, the feeding of the raw material oxygen is cut off emergently.
When the pressure in the oxidative esterification reactor exceeds 0.45MPa, the reflux amount of cold methanol is increased to 3.2 times of the original reflux amount. And on the basis of increasing the reflux quantity of the cold methanol, the oxygen feeding is cut off at the same time, and the reaction is stopped. And filling nitrogen for replacement in an emergency.
And when the pressure in the oxidation esterification reactor is reduced to 0.25MPa, the cold methanol reflux is recovered to the original reflux, the methanol flow is recovered to the original flow, the nitrogen filling is stopped, the oxygen is introduced again, and the original production flow is recovered.
The method is adopted to produce methyl nitrite from synthesis gas, and the operation is stably carried out for 5000 hours in total. When the operation is finished, the temperature in the oxidation esterification reactor is 35 ℃, the pressure is 0.23MPa, the conversion rate of reaction raw materials is 96 percent, and the consumption of nitrogen is 0.5 ten thousand meters3。
During the operation, 2 times of overtemperature and 1 time of overpressure are totally generated in the oxidation esterification reactor. Wherein, the overtemperature respectively occurs at 3200h and 4500h after the operation is started, and the temperature in the reactor is 52 ℃ and 58 ℃ in sequence. Overpressure occurred at 4500h after start of run, and the pressure inside the reactor was 0.43 MPa.
Example 3
The reaction conditions of oxidative esterification are that the temperature is 45 ℃, the pressure is 0.24MPa, and the molar ratio of methanol to nitric oxide to oxygen is 130: 18: 6, the reflux quantity of the cold methanol is more than 90 percent of the original flow quantity. While controlling the temperature and/or pressure within the oxidative esterification reactor in the following manner.
When the temperature in the oxidation esterification reactor reaches 45 ℃, the reflux quantity of the cold methanol is increased to 1.6 times of the original reflux quantity. And meanwhile, when the flow of the methanol is lower than 80% of the original flow, generating a methanol low-flow alarm, and increasing the flow of the methanol to 130% of the original flow. When the flow rate of the methanol is lower than 70 percent of the original flow rate, the feed of the raw material oxygen is cut off in an emergency.
When the temperature in the oxidation esterification reactor reaches 55 ℃, the reflux quantity of the cold methanol is increased to 2.2 times of the original reflux quantity. And on the basis of increasing the reflux quantity of the cold methanol, the oxygen feeding is cut off at the same time, and the reaction is stopped. Meanwhile, nitrogen is filled in emergently for replacement.
When the temperature in the oxidation esterification reactor is reduced to 50 ℃, the cold methanol reflux is recovered to the original reflux, the methanol flow is recovered to the original flow, the nitrogen filling is stopped, the oxygen is introduced again, and the original production flow is recovered.
When the pressure in the oxidation esterification reactor reaches 0.28MPa, the reflux quantity of the cold methanol is increased to 1.5 times of the original reflux quantity. Meanwhile, when the flow of the methanol is lower than 80% of the original flow, a methanol low-flow alarm is generated, and the flow of the methanol is increased to 130% of the original flow; and when the flow rate of the methanol is lower than 70 percent of the original flow rate, the feeding of the raw material oxygen is cut off emergently.
When the pressure in the oxidative esterification reactor exceeds 0.35MPa, the reflux amount of cold methanol is increased to 2 times of the original reflux amount. And on the basis of increasing the reflux quantity of the cold methanol, the oxygen feeding is cut off at the same time, and the reaction is stopped. And filling nitrogen for replacement in an emergency.
And when the pressure in the oxidation esterification reactor is reduced, the cold methanol reflux is recovered to the original reflux, the methanol flow is recovered to the original flow, the nitrogen filling is stopped, the oxygen is introduced again, and the original production flow is recovered.
The method is adopted to produce methyl nitrite from synthesis gas, and the operation is stably carried out for 6500h in total. When the operation is finished, the temperature in the oxidation esterification reactor is 45 ℃, the pressure is 0.25MPa, the conversion rate of reaction raw materials is 97 percent, and the consumption of nitrogen is 0.43 ten thousand meters3。
During the operation, 3 times of overtemperature and 2 times of overpressure are totally generated in the oxidation esterification reactor. Wherein, overtemperature respectively appears at 2800h, 3900h and 5500h after the operation is started, and when the overtemperature condition occurs, the temperature in the reactor is 50 ℃, 53 ℃ and 49 ℃ in sequence. Overpressure appears at 2800h, 3900h and 5500h after the operation is started, and when the overpressure condition occurs, the pressure in the reactor is 0.35MPa, 0.4MPa and 0.29MPa in sequence.
Example 4
The same embodiment as that of example 1 is adopted, except that 6 oxygen gas injection ports are arranged in the oxidation esterification reactor respectively from 1/7, 2/7, 3/7, 4/7, 5/7 and 6/7 in the longitudinal height direction, and the oxygen gas is fed from the inlet to the outlet in a ratio of 6: 5: 4: 3:2: 1.
the method is adopted to produce methyl nitrite from synthesis gas, and the operation is stable for 3000 hours in total. When the reaction is finished, the temperature in the oxidation esterification reactor is 35 ℃, the pressure is 0.23MPa, the conversion rate of reaction raw materials is 97.8 percent, and the consumption of nitrogen is 0.35 ten thousand meters3。
During the operation, 2 times of overtemperature and 1 time of overpressure are totally generated in the oxidation esterification reactor. The overtemperature appears at 1100h and 2900h after the start of the operation, and when the overtemperature occurs, the temperature in the reactor is 46 ℃ and 51 ℃ in sequence. Overpressure occurred at 2900h after start of run, and the reactor pressure was 0.31MPa when overpressure occurred.
Example 5
The same embodiment as in example 1 was used except that the oxygen feed amount per oxygen inlet was the same.
The method is adopted to produce methyl nitrite from synthesis gas, and the operation is stable for 3000 hours in total. When the reaction is finished, the temperature in the oxidation esterification reactor is 43 ℃, the pressure is 0.42MPa, the conversion rate of reaction raw materials is 92 percent, and the consumption of nitrogen is 1.2 ten thousand m3。
During the operation, 5 times of overtemperature and 3 times of overpressure are totally appeared in the oxidation esterification reactor. Wherein, the overtemperature respectively appears at 520 th, 650 th, 1200 th, 1890 th and 2500 th after the operation is started, and when the overtemperature condition occurs, the temperature in the reactor is 47 ℃, 49 ℃, 52 ℃, 46 ℃ and 57 ℃ in sequence. Overpressure appears at 650 th, 1200 th and 2500 th hours after the operation is started, and when the overpressure condition occurs, the pressure in the reactor is 0.34MPa, 0.41MPa and 0.46MPa in sequence.
Comparative example 1
The oxidative esterification conditions of example 1 were followed except that the prior art oxidative esterification reactor was used for syngas to ethylene glycol production. When the temperature in the reactor exceeds 55 ℃ or the pressure exceeds 0.28MPa, the reaction device is closed, the reaction is stopped, and the reaction is resumed until the temperature in the reactor recovers 45 ℃ or the pressure recovers 0.2 MPa.
The reaction is carried out for 3000 hours (including the reaction stopping time in the midway), when the reaction is finished, the temperature in the oxidation esterification reactor is 45 ℃, the pressure is 0.24MPa, the conversion rate of the reaction raw materials is 92%, the reaction is stopped for 5 times in the period, and the reaction device is closed for 20.5 hours in total.
During the operation, the inside of the oxidation esterification reactor is overtemperature for 4 times and overpressure for 5 times in total. The overtemperature respectively appears at 550h, 1700h, 1900h and 2500h after the operation is started, when the overtemperature condition occurs, the temperature in the reactor is 56 ℃, 57 ℃, 56 ℃ and 59 ℃, and the time for closing the reaction device each time is 3h, 4h, 4.5h and 6 h. Overpressure appears at 300h, 550h, 1700h, 1900h and 2500h after the operation is started, when the overpressure condition occurs, the pressure is 0.29MPa, 0.33MPa, 0.31MPa, 0.37MPa and 0.41MPa in sequence, and the time for closing the reaction device each time is 3h, 4h, 4.5h and 6h respectively.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. A method for safely preparing methyl nitrite in an oxidative esterification reactor, the method comprising: introducing fresh methanol, nitric oxide and oxygen into an oxidation esterification reactor to carry out oxidation esterification reaction at a set temperature T and a set pressure P, wherein unreacted gas phase is used for recovering the methanol, and recovered cold methanol is refluxed to the oxidation esterification reactor to participate in the oxidation esterification reaction, and the method is characterized by comprising the steps of measuring the temperature and/or the pressure in the oxidation esterification reactor regularly or irregularly, and controlling the temperature and/or the pressure in the oxidation esterification reactor according to the measurement result by adopting the following hierarchical control mode so that the temperature in the oxidation esterification reactor is maintained at T and/or the pressure in the oxidation esterification reactor is maintained at P:
increasing the amount of recovered cold methanol reflux when the temperature is T1 or the pressure is P1;
when the temperature is T2 or the pressure is P2, the reflux amount of the recovered cold methanol is increased and the reaction is stopped;
wherein T is more than T1 and less than T2, and T2-T is more than or equal to 30 ℃;
p is more than P1 and more than P2, and P2-P is more than or equal to 0.17 MPa.
2. The method of claim 1, further comprising monitoring and adjusting the flow of fresh methanol when the temperature is T1 or the pressure is P1.
3. The process of claim 1 wherein, when the temperature is T1, the amount of recovered cold methanol reflux is increased while monitoring and adjusting the fresh methanol flow rate; or
When the temperature is T2, increasing the reflux quantity of the recovered cold methanol, cutting off the oxygen feeding and filling inactive gas for replacement, and stopping the reaction; or
When the pressure is P1, the return flow of recovered cold methanol is increased while the flow of fresh methanol is monitored and adjusted; or
When the pressure is P2, the amount of recovered cold methanol reflux is increased while the oxygen feed is cut off and replaced with inert gas, and the reaction is stopped.
4. The method of claim 1 or 3, wherein the non-reactive gas comprises: at least one of nitrogen, helium, argon, and carbon dioxide.
5. The process of claim 1, wherein the conditions of the oxidative esterification reaction comprise: setting the temperature T to be 20-55 ℃, setting the pressure P to be 0.1-0.28MPa, and the molar ratio of the fresh methanol to the nitric oxide to the oxygen is 200: 1-40: 1-10, the reflux quantity of the recovered cold methanol is 0.25-0.98 of the total methanol feed, and the temperature of the recovered cold methanol is-15 ℃ to 30 ℃.
6. The process of claim 1 or 3, wherein 55 ℃ < T1 ≤ 65 ℃, the reflux of recovered methanol is increased to 1.6-2.5 times the original reflux while monitoring the fresh methanol flow, and when the fresh methanol flow is 70-80% of the original flow, the fresh methanol flow is increased to 90-120% of the original flow; when the fresh methanol flow is lower than 70% of the original flow, the oxygen feed is cut off.
7. A process according to claim 1 or claim 3 wherein the recovered cold methanol reflux is increased to 2.2 to 3.6 times the original reflux at 65 ℃ T2 ≦ 75 ℃.
8. A process according to claim 1 or claim 3 wherein T2 > 75 ℃ and the reflux of recovered cold methanol is increased to 3.2 to 5.6 times the original reflux.
9. The process of claim 1 or 3, wherein 0.28MPa < P1 ≤ 0.35MPa, the reflux amount of recovered cold methanol is increased to 1.5-2 times of the original reflux amount, while the flow rate of fresh methanol is monitored, and when the flow rate of fresh methanol is 70-80% of the original flow rate, the flow rate of fresh methanol is increased to 90-120% of the original flow rate; (ii) a When the fresh methanol flow is lower than 70% of the original flow, the oxygen feed is cut off.
10. A process according to claim 1 or 3, wherein 0.35MPa < P2 ≤ 0.45MPa and the reflux of recovered cold methanol is increased to 2-3.2 times the original reflux.
11. A process according to claim 1 or claim 3 wherein P2 > 0.45MPa and the reflux of recovered cold methanol is increased to 3-5.3 times the original reflux.
12. The process of claim 1, wherein the process further comprises dividing the oxygen into 3-20 oxygen streams, and feeding the oxygen streams into different positions in the oxidative esterification reactor to participate in the oxidative esterification reaction, wherein the feeding amount of each oxygen stream is the same or different.
13. The process of claim 12, wherein the oxygen feed ports are respectively provided at 1/(n +1), 2/(n +1), 3/(n +1), 4/(n +1) … n/(n +1) positions in the height direction of the oxidative esterification reactor, and the feed amount of each oxygen is different, and the ratio from inlet to outlet is: n: n-1: n-2: …:1, n being the number of oxygen feed streams.
14. An apparatus for producing ethylene glycol from synthesis gas, the apparatus comprising an oxidative esterification reactor with temperature and/or pressure control by the process of any one of claims 1 to 13.
15. Use of the method of any one of claims 1 to 13 and/or the apparatus of claim 14 in a process for the preparation of ethylene glycol from synthesis gas.
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