CN114177950B - Preparation method of dialkyl carbonate, catalyst regeneration method, catalyst regeneration device and application of dialkyl carbonate - Google Patents
Preparation method of dialkyl carbonate, catalyst regeneration method, catalyst regeneration device and application of dialkyl carbonate Download PDFInfo
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- 238000011069 regeneration method Methods 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 230000008929 regeneration Effects 0.000 title claims abstract description 86
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 241000282326 Felis catus Species 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001339 alkali metal compounds Chemical group 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 54
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 14
- 238000006606 decarbonylation reaction Methods 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000006324 decarbonylation Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- -1 copper halides Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of dialkyl carbonate, a catalyst regeneration method and device thereof and application. The catalyst regeneration method comprises the step of contacting the catalyst to be regenerated with steam until the generation rate of carbon monoxide in the regenerated tail gas is less than 50 mL/h.g.cat. The regeneration method can accurately judge the regeneration end point, the regenerated catalyst has stable performance and good catalytic effect, and the service life of the catalyst is obviously prolonged.
Description
Technical Field
The invention relates to a method and a device for regenerating dialkyl carbonate catalyst and application thereof, and a method and a device for preparing dialkyl carbonate and application thereof.
Background
The dimethyl carbonate is used as a nontoxic organic raw material, can perform various chemical reactions such as carbonylation, methylation, methoxylation, carboxymethylation and the like, and has wide application market and prospect.
The existing industrial production process of dimethyl carbonate mainly comprises a phosgene method, a transesterification method, a methanol oxidative carbonylation method and the like. The phosgene method is an early production method, has complex process and high toxicity of raw materials, is unfavorable for safe production, and belongs to a obsolete process. CN103143357a and CN107694609a provide a process for preparing dimethyl carbonate by the oxidative carbonylation of methanolCatalyst, the former catalyst comprises active component Cu 2 O and activated carbon, the latter catalysts include copper halides and ionic liquids, but both catalysts have lower methanol conversion and higher cost of preparation or more severe operating conditions, severely limiting their use. CN109821560a discloses a catalyst for producing dimethyl carbonate by transesterification and a using method thereof, and the method has the advantages of high selectivity of dimethyl carbonate and simple operation; however, the raw material ethylene carbonate is derived from petroleum resources, the price and the yield are easy to fluctuate, and the economic benefit is directly influenced. In addition, CN102212009a discloses a process for co-producing dimethyl carbonate and dimethyl ether by urea alcoholysis; CN106946706a discloses a method for preparing dimethyl carbonate by directly reacting carbon dioxide and methanol, but both methods have the problems of harsh conditions, low yield and the like, and the realization of industrialization is still difficult.
The development of the carbon-chemical industry not only meets the energy requirement, but also can realize the efficient utilization of coal, greatly reduces the environmental pollution, and is a very important research field. CN106518675a and CN106431920B provide a process for preparing dimethyl oxalate from synthesis gas. The reaction can efficiently obtain high-purity dimethyl oxalate.
Dimethyl oxalate can be conveniently obtained through decarbonylation reaction, and the reaction equation is as follows:
。
patent TW513405B discloses a process for preparing dialkyl carbonates. The patent uses a supported alkali metal catalyst to catalyze the decarbonylation reaction of dialkyl oxalate to produce dialkyl carbonate. The catalyst can simultaneously obtain high conversion rate and selectivity, wherein the alkali metal catalyst loaded by taking activated carbon as a carrier has the most application prospect. However, experiments show that the activity of this type of catalyst is significantly reduced after a period of reaction. The catalytic activity of the catalyst cannot be recovered by common methods such as heating, flushing, ultrasonic treatment, reloading active components and the like. The high temperature steam treatment can remove the carbon compound attached to the surface of the catalyst generated in the reaction process, so that the covered active center of the catalyst is exposed again, and the activity is recovered. However, since the catalyst carrier is also a carbon material, the catalyst is liable to undergo reaction under the condition of water vapor regeneration, resulting in loss and change of the catalyst. The conventional treatment mode can avoid deep reaction to a certain extent by controlling the temperature, but the regeneration end point is difficult to accurately judge, the risk of damaging the catalyst still exists, the regenerated catalyst has the problem of incomplete recovery or excessive reaction, the regenerated catalyst has unstable performance and poor catalyst effect. Thus, there is a need for a simple and efficient method to control the progress of the reaction and the regeneration of the catalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a regeneration method of a dialkyl carbonate catalyst, by adopting the regeneration method, the regeneration end point can be accurately judged, the regenerated catalyst has stable performance and good catalytic effect, and the service life of the catalyst is obviously prolonged.
In a first aspect, the invention provides a method for regenerating a dialkyl carbonate catalyst comprising contacting the catalyst to be regenerated with steam until the rate of carbon monoxide production in the regenerated tail gas is less than 50 mL/h.g.cat.
In the present invention, the unit "mL/h.g.cat" means the amount of milliliters produced per hour per gram of catalyst. For example, a carbon monoxide production rate of 10mL/h.g.cat means that 10mL of carbon monoxide is produced per hour per gram of catalyst.
In the invention, the carbon monoxide generation rate is calculated as follows: carbon monoxide formation rate= (regeneration off-gas flow x carbon monoxide content)/catalyst weight.
According to some embodiments of the regeneration process of the present invention, the rate of carbon monoxide production in the regeneration tail gas is no greater than 30mL/h.g.cat, preferably no greater than 10mL/h.g.cat.
According to some embodiments of the regeneration method of the present invention, the regeneration conditions include: space velocity of 0.5-5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature rising rate is 1-5 ℃/min, and the temperature rises to 300-600 ℃.
According to some embodiments of the regeneration process of the present invention, the regeneration process further comprises introducing nitrogen and/or an inert gas. This gas is beneficial to promote vaporization of the water. For example, the catalyst to be regenerated is contacted with steam and a gas, which is nitrogen and/or an inert gas. Preferably the molar ratio of gas to water vapour is from 0.1 to 5:1.
according to some embodiments of the regeneration process of the present invention, the catalyst is a dialkyl oxalate decarbonylation catalyst for the preparation of dialkyl carbonate.
According to some embodiments of the regeneration process of the present invention, the catalyst comprises an activated carbon support and an active component.
According to some embodiments of the regeneration method of the present invention, the carrier is selected from one or more of coconut shell activated carbon, coal activated carbon, and fruit shell activated carbon.
According to some embodiments of the regeneration method of the present invention, the active component is selected from alkali metal compounds containing one or more of potassium, rubidium and cesium.
According to some embodiments of the regeneration process of the present invention, preferably, the weight of the support is 60 to 95 wt% and the weight of the active component is 5 to 40 wt% based on the total weight of the catalyst.
According to some embodiments of the regeneration process of the present invention, preferably, the catalyst is a supported catalyst, typical preparation methods include, but are not limited to, impregnation methods. Such as isovolumetric infusion, etc.
In a second aspect, the invention provides a device for regenerating a dialkyl carbonate catalyst, comprising a regeneration reactor, a steam feed line and a regeneration tail gas line, wherein the steam feed line and the regeneration tail gas line are communicated with the regeneration reactor, and the regeneration tail gas line is connected with a carbon monoxide detector.
According to some embodiments of the regeneration device of the present invention, the regeneration device further comprises a first valve disposed on the vapor feed line and a second valve disposed on the regeneration tail line. Preferably, the first valve and the second valve are interlocked.
According to some embodiments of the regeneration device of the present invention, the detector may preferably detect the content of carbon monoxide or the like.
According to some embodiments of the regeneration device of the present invention, the detector may be a chromatograph or the like.
The third aspect of the present invention provides a method for preparing a dialkyl carbonate: the method comprises the following steps:
(1) Under the action of a catalyst, the raw materials undergo decarbonylation reaction to generate dialkyl carbonate until the catalyst needs to be regenerated;
(2) Switching to a regeneration process using the above-described regeneration method or the above-described regeneration apparatus;
and (3) circulating the step (1) and the step (2) to carry out continuous production.
According to some embodiments of the method of preparation of the invention, the feedstock is a feedstock containing dialkyl oxalate.
According to some embodiments of the preparation method of the present invention, in the step (1), the condition for determining that the catalyst needs to be regenerated may be determined according to the need, for example, the conversion rate of dimethyl oxalate is reduced to 80%, and the content of dimethyl oxalate in the corresponding reactor outlet product is 3.2% by weight. Therefore, the content of oxalic acid dialkyl in the material at the outlet of the reactor is more than 3.2 percent, which is taken as the basis for judging that regeneration is needed.
According to some embodiments of the methods of preparation of the present invention, the decarbonylation reaction conditions include: the temperature is 165-230 ℃ and the airspeed is 0.5-10h -1 。
According to some embodiments of the preparation method of the present invention, the catalyst is a dialkyl oxalate decarbonylation catalyst for preparing dialkyl carbonate.
According to some embodiments of the preparation method of the present invention, the catalyst comprises an activated carbon support and an active component.
According to some embodiments of the method of preparation of the present invention, the carrier is selected from one or more of coconut shell activated carbon, coal activated carbon, and fruit shell activated carbon.
According to some embodiments of the preparation method of the present invention, the active component is selected from alkali metal compounds containing one or more of potassium, rubidium and cesium.
According to some embodiments of the preparation process according to the invention, the weight of the support is preferably 60 to 95% by weight and the weight of the active component is preferably 5 to 40% by weight, based on the total weight of the catalyst.
According to some embodiments of the preparation process of the present invention, preferably, the catalyst is a supported catalyst, typical preparation processes include, but are not limited to, impregnation processes. Such as isovolumetric infusion, etc.
According to some embodiments of the preparation methods of the present invention, the preparation method of dialkyl carbonate may comprise the steps of:
(1) In the normal dialkyl oxalate decarbonylation reaction stage, the raw material of the feeding part is the raw material containing dialkyl oxalate component according to the proportion of 0.5-10.0h -1 Inputting the raw materials into a reaction system, wherein the temperature of a catalyst bed in a reactor is 165-230 ℃, after the raw materials react under the action of a catalyst, detecting the content of dialkyl oxalate in the product through analysis of a detection part, and continuously carrying out the reaction when the content is not more than a limit value; when the content of the dialkyl oxalate exceeds a limit value, the catalyst needs to be regenerated;
(2) Switching the raw materials into water according to 0.5-5.0 hr -1 Is introduced into the reactor. And raising the catalyst bed temperature to a regeneration temperature of 300-600 ℃ at a rate of 1-5 ℃/min and keeping constant. After the catalyst bed temperature reached the specified temperature and maintained at a constant temperature, the flow of carbon monoxide in the reactor outlet gas was detected. When the rate of carbon monoxide production is less than 50mL/h.g.cat, preferably not more than 30mL/h.g.cat, more preferably not more than 10 mL/mL/h.g.cat, the catalyst bed temperature is slowly lowered to the reaction temperature and water is switched to the raw material containing dialkyl oxalate to resume the normal reaction.
According to a fourth aspect of the present invention there is provided an apparatus for producing dialkyl carbonate comprising a reactor, and a feed line and a tail gas line in communication with the reactor, the feed line being in communication with a supply of reaction material and/or a source of water, the tail gas line being connected to a detector for detecting dialkyl oxalate and/or carbon monoxide in the material at the outlet of the reactor.
According to some embodiments of the preparation apparatus of the present invention, the reaction raw material is a raw material containing dialkyl oxalate.
According to some embodiments of the preparation apparatus of the present invention, preferably, the detector may detect the content of dialkyl oxalate and/or carbon monoxide, etc.
According to some embodiments of the preparation device of the present invention, the detector may be a chromatograph or the like.
According to some embodiments of the production apparatus of the present invention, the reactor may be a continuous feed reactor, such as, but not limited to, a continuous feed tubular reactor.
According to some embodiments of the preparation apparatus of the present invention, the catalyst used may be placed in a constant temperature section inside the reactor.
In a fifth aspect, the present invention provides the use of the above-described regeneration method, the above-described regeneration device, the above-described preparation method or the above-described preparation device for decarbonylating a dialkyl oxalate to prepare a dialkyl carbonate.
The invention has the beneficial effects that:
(1) Because the carbon deposit and the carrier have different structures and compositions, the reaction rate with the water vapor is also different, and the regeneration method and/or the regeneration device can judge the regeneration end point in time and terminate the regeneration operation to protect the catalyst.
(2) The dialkyl carbonate preparation method and/or the preparation device can conveniently grasp the variation trend of the catalyst performance and timely finish the recovery of the catalyst performance, so that the decarbonylation reaction of the dialkyl oxalate can keep higher conversion rate, the service life of the catalyst is obviously prolonged, the defects of long regeneration time, unstable effect and the like of the catalyst are avoided, and the dialkyl carbonate preparation method and/or the preparation device have good application prospects.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
In the following examples and comparative examples,
(1) The catalyst for preparing dialkyl carbonate from dialkyl oxalate is a catalyst which is prepared by an isovolumetric impregnation method and is loaded on coconut shell activated carbon, wherein the weight content of potassium carbonate is 25 percent.
(2) The reaction raw material is methanol solution with the dimethyl oxalate content of 20 weight percent, the conversion rate of the dimethyl oxalate is reduced to 80 percent, which is used as a standard that the catalyst needs to be regenerated, and the corresponding dimethyl oxalate content in the outlet product of the reactor is 3.2 weight percent.
(3) In the examples, the content of carbon monoxide in the regenerated off-gas noncondensable gas was 0.8% by volume, except for the specific explanation, when the carbon monoxide production rate was 10mL/h.g.cat. Therefore, when the content of carbon monoxide in the regenerated tail gas after gas-liquid separation is less than 0.8 volume percent, the regeneration operation is stopped, and the normal reaction is restored.
(4) The chromatographs for analysis of the liquid and gas phase products were 7890B type chromatography from Agilent corporation and T3000 type chromatography from SRA instrums corporation, respectively.
[ example 1 ]
(1) Reaction stage for preparing dialkyl carbonate by decarbonylation of dialkyl oxalate
10g of dialkyl oxalate catalyst for preparing dialkyl carbonate is placed in the middle of a tubular reactor, the temperature is increased to 180 ℃, and the reaction pressure is normal pressure. Dimethyl oxalate in methanol was added for 1.0h -1 Is introduced into the reactor and is vaporized to reach the catalyst bed. The reaction product was subjected to chromatography, wherein the content of dimethyl oxalate was 0.2% by weight, and the conversion of dimethyl oxalate was 98.7% by calculation. After 15 days of continuous reaction, the dimethyl oxalate content in the reactor outlet product reached 3.4 wt.%, and the catalyst needed to be regenerated.
(2) Catalyst regeneration stage
Stop feeding for 2.0h -1 Deionized water was fed while nitrogen was fed to the reactor at a rate of 200mL/min (molar ratio of gas to water vapor 0.48:1). The temperature of the bed was gradually increased to 300℃at a rate of 1℃per minute and kept stable. The content of carbon monoxide in the regenerated tail gas at the outlet of the reactor was periodically detected, and it was found that the carbon monoxide production rate was 10mL/h.g.cat after 12 hours.
(3) Circulating the step (1) and the step (2) to perform continuous production stages
Slowly reducing the temperature of the catalyst bed to 180 ℃, switching the feeding material into a methyl alcohol solution of dimethyl oxalate, and continuing the reaction according to the reaction condition of the step (1), so that the catalyst performance is recovered.
After 6 reaction and regeneration cycles are accumulated for 3 months, the catalyst activity is slightly reduced, and the conversion rate of the initial dimethyl oxalate is reduced to 96.1 percent.
[ example 2 ]
The reaction was carried out according to step (1) [ example 1 ]. Different, the reaction temperature is changed to 165 ℃, and the space velocity of the dimethyl oxalate raw material is changed to 0.5h -1 The reaction was continued for 32 days, and the dimethyl oxalate content in the reactor outlet product reached 3.2%, starting the catalyst regeneration operation.
Regeneration is performed according to step (2) [ example 1 ]. Except that the regeneration temperature was changed to 500℃and the carbon monoxide production rate was 10mL/h.g.cat after 5 hours.
The catalyst performance is effectively recovered, and the reaction proceeds. The catalyst performance did not decrease after 4 reactions and regeneration cycles accumulated over 4 months.
[ example 3 ]
The reaction and regeneration were carried out in the same manner as in example 1 except that the regeneration temperature in step (2) was changed to 600℃and the carbon monoxide production rate after 4 hours of regeneration was 10mL/h.g.cat.
After 6 reactions and regeneration cycles are accumulated for more than 2 months, the initial activity of the catalyst does not decrease, but the regeneration cycle is reduced to 10 days, and the regeneration is more frequent.
[ example 4 ]
The reaction and regeneration were carried out in the same manner as in example 1, except that in step (2), the regeneration operation was terminated by lowering the catalyst bed temperature with the carbon monoxide production rate of 30mL/h.g.cat as a criterion for completion of the regeneration.
After 6 reaction and regeneration cycles are accumulated for more than 3 months, the initial activity of the catalyst is reduced, and the conversion rate of dimethyl oxalate is 93.6%.
[ example 5 ]
The reaction and regeneration were carried out as described in [ example 1 ], except that in step (2), nitrogen gas (molar ratio of gas to water vapor: 4.82:1) was introduced into the reactor at a flow rate of 2000 mL/min.
After 6 reaction and regeneration cycles are accumulated for more than 3 months, the initial activity of the catalyst is reduced, and the conversion rate of dimethyl oxalate is 94.7%.
[ example 6 ]
The reaction and regeneration were carried out as described in [ example 1 ], except that the regeneration temperature in step (2) was lowered to 200 ℃.
Again, the conversion of dimethyl oxalate was 83% and the catalyst performance was not recovered.
[ example 7 ]
The reaction and regeneration were carried out as described in [ example 1 ], except that the regeneration temperature of step (2) was increased to 700 ℃.
Again, the conversion of dimethyl oxalate was 91.2% and the catalyst performance was not fully recovered.
[ comparative example 1 ]
The reaction and regeneration were carried out in the same manner as in example 1, except that in step (2), the regeneration operation was terminated by lowering the catalyst bed temperature with the carbon monoxide production rate of 50mL/h.g.cat as a criterion for completion of the regeneration.
Again, the conversion of dimethyl oxalate was 89.8% and the catalyst performance was not fully recovered.
[ comparative example 2 ]
The reaction and regeneration were carried out in the same manner as in example 2, except that the change in the carbon monoxide content in the regeneration off-gas was not detected during the regeneration in step (2), and the regeneration time was set to 12 hours. Again, the dimethyl oxalate conversion was 85% and the regeneration effect was not ideal, indicating that water vapor was over-reacted with the catalyst.
[ comparative example 3 ]
The procedure of step (2) regeneration is as follows:
nitrogen was introduced into the reactor at a flow rate of 200 mL/min. The bed temperature was gradually increased to 300℃at a rate of 1℃per minute, and the temperature was kept stable, and after 12 hours of reaction, the regeneration was stopped.
Again, the conversion of dimethyl oxalate was 79% and the catalyst performance was not recovered.
[ comparative example 4 ]
The catalyst obtained in [ comparative example 3 ] was repeatedly washed with methanol at 60℃and dried, and then again evaluated, whereby the catalyst was inactive. The organic solvent is used for washing, so that the influence of carbon deposition is not eliminated, active components on the catalyst are dissolved, the active components are lost, and the catalyst is thoroughly deactivated.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (9)
1. A method for regenerating dialkyl carbonate catalyst includes such steps as contacting the catalyst to be regenerated with steam until the rate of generation of CO in regenerated tail gas is less than 50mL/h.g.cat,
wherein the catalyst is a catalyst for preparing dialkyl carbonate by decarbonylating dialkyl oxalate;
the catalyst comprises an active carbon carrier and an active component;
the carrier is selected from one or more of coal activated carbon and shell activated carbon;
the active component is selected from alkali metal compounds containing one or more of potassium, rubidium and cesium,
the regeneration conditions include: space velocity of 0.5-5h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the heating rate is 1-5 ℃/min; and/or, heating to 300-600 ℃,
the regeneration method also comprises the step of introducing inert gas.
2. The regeneration process according to claim 1, wherein the carbon monoxide production rate in the regeneration tail gas is not more than 30mL/h.g.cat.
3. The regeneration process according to claim 1, wherein the carbon monoxide production rate in the regeneration tail gas is not more than 10mL/h.g.cat.
4. A regeneration process according to any one of claims 1 to 3, further comprising introducing nitrogen.
5. The regeneration process according to claim 4, characterized in that the molar ratio of gas to water vapor is between 0.1 and 5:1.
6. a regeneration process according to any one of claims 1 to 3, characterized in that the carrier is selected from coconut activated carbon.
7. A dialkyl carbonate catalyst regeneration device, comprising a regeneration reactor, a steam feed line and a regeneration tail gas line which are communicated with the regeneration reactor, wherein the regeneration tail gas line is connected with a carbon monoxide detector; wherein the regeneration device employs the regeneration method according to any one of claims 1 to 6.
8. The regeneration device of claim 7, further comprising a first valve disposed on the vapor feed line and a second valve disposed on the regeneration tail line.
9. The regeneration device of claim 8, wherein the first valve and the second valve are in linkage.
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