CN111606805B - Production process and device for co-producing dimethyl carbonate by coal-to-ethylene glycol device - Google Patents
Production process and device for co-producing dimethyl carbonate by coal-to-ethylene glycol device Download PDFInfo
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 42
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000003245 coal Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 7
- 238000002309 gasification Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 25
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 25
- 238000004064 recycling Methods 0.000 claims description 14
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 238000006462 rearrangement reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
- Y02P20/141—Feedstock
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Abstract
The invention discloses a production process and a device for co-producing dimethyl carbonate by a coal-to-ethylene glycol device, wherein the ethylene glycol device comprises a methyl nitrite production part and a carbon monoxide production part by coal gasification; mixing carbon monoxide and methyl nitrite, controlling the temperature to be 100-145 ℃ and the pressure to be less than or equal to 0.3Mpa, and carrying out the synthesis reaction of the dimethyl carbonate under the action of a composite catalyst; and (3) carrying out gas-liquid separation rectification on the reacted materials, directly discharging the separated gas containing nitric oxide, and leading the rectified liquid out to a refining process for refining to obtain the dimethyl carbonate. The process can realize safe and stable long-period operation of the dimethyl carbonate device; the product chain in the production of ethylene glycol is prolonged, and the dimethyl carbonate product is increased; meanwhile, nitric oxide which is a byproduct generated in the production process of the dimethyl carbonate device can be returned to the ethylene glycol device, materials are comprehensively recycled, and the effects of energy conservation and consumption reduction are obvious.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a production process and a device for co-producing dimethyl carbonate by a coal-to-ethylene glycol device.
Background
The coal-to-ethylene glycol device produces carbon monoxide through coal gasification, and after pressure swing adsorption, a large amount of high-purity carbon monoxide gas raw materials are obtained; methyl nitrite, which is the raw material for producing ethylene glycol, is synthesized with methanol and oxygen and Nitric Oxide (NO) prior to ethylene glycol synthesis. In order to adapt to market changes, the device is kept to run safely and stably for a long period of time under full load, and the product chain is prolonged to be a stable solution.
CN101462961a discloses a process flow for producing ethylene glycol and co-producing dimethyl carbonate, which is a linking process flow for synthesizing ethylene glycol and co-producing dimethyl carbonate by using carbon monoxide and methyl nitrite as initial raw materials. However, in practice, it is a byproduct of dimethyl carbonate from a glycol plant, which itself is a byproduct of dimethyl carbonate, and the main product ratio is 33.6wt% of dimethyl oxalate, 17.9wt% of dimethyl carbonate, 48.1wt% of methanol, and the formation of dimethyl carbonate is a gas phase oxidative coupling reaction, and the selectivity of the catalyst used in the reaction is poor, and the yield and purity of dimethyl carbonate are low.
Disclosure of Invention
The invention provides a production process and a production device for co-producing dimethyl carbonate by a coal-to-ethylene glycol device, wherein the dimethyl carbonate can safely and stably run for a long period under full load; the product chain in the production of ethylene glycol is prolonged, and the dimethyl carbonate product is increased; so that the device system saves energy and reduces consumption.
The technical scheme of the invention is that the production process for co-producing dimethyl carbonate by a coal-to-ethylene glycol device comprises the following steps:
1) The ethylene glycol device comprises a methyl nitrite production part and a carbon monoxide production part by coal gasification; carbon monoxide is mixed with methyl nitrite under nitrogen atmosphere after pressure swing adsorption, then preheating is carried out, a small amount of hydrogen chloride gas is added for mixing, the volume concentration of the hydrogen chloride gas is less than 200ppm, finally the mixed gas enters a reactor, the temperature is controlled to be 100-145 ℃, the pressure is less than or equal to 0.3Mpa, and the synthesis reaction of the dimethyl carbonate is carried out under the action of a composite catalyst;
2) And (2) feeding the materials after the synthesis reaction in the step (1) into a rectifying tower, carrying out gas-liquid separation through rectification at the temperature of 120-180 ℃, directly discharging the gas after rectification treatment containing nitric oxide, and leading the liquid after rectification out to a refining process for refining to obtain the dimethyl carbonate.
Further, the purity of the carbon monoxide after pressure swing adsorption is 99.0 to 99.5 percent, and the molar ratio of the carbon monoxide to the methyl nitrite is 1.7 to 2.5:0.8 to 1.1; the nitrogen accounts for more than 40 percent of the total volume of the carbon monoxide and the methyl nitrite.
Further, the moisture in the hydrogen chloride gas is less than or equal to 30ppm.
Further, the composite catalyst in the step 1) takes spinel-structured porous lithium aluminate as a carrier, and is loaded with 1-2wt% of palladium chloride, 3-15wt% of copper chloride and 0.1-0.2wt% of nano-scale cerium oxide.
Further, the spinel-structured porous lithium aluminate is added with 5% by mass of the polycarboxylic acid and uniformly mixed before the catalyst is supported.
Further, the exhaust gas in the step 2) contains nitric oxide, and is introduced into a methyl nitrite production part of an ethylene glycol production device for recycling; part of the liquid separated by rectification is sent to the subsequent refining process, and the other part is heated and then enters the rectification process again for recycling.
The invention also relates to a production device for co-producing dimethyl carbonate by using the coal-to-ethylene glycol device, which comprises the coal-to-ethylene glycol device, wherein a methyl nitrite production system and a coal gasification carbon monoxide production system are arranged in the device, a carbon monoxide pipeline of the carbon monoxide system is connected with a methyl nitrite pipeline of the methyl nitrite production system after passing through pressure swing adsorption equipment and is introduced into a synthesis reactor, a discharge port of the synthesis reactor is connected to a feed port of a rectifying tower through a pipeline, and a gas outlet at the upper part of the rectifying tower is connected to a gas inlet of the methyl nitrite production system; the rectifying tower is also provided with a circulating system, and a liquid outlet at the bottom of the rectifying tower is connected to a liquid return port of the circulating system through a pipeline and a pump; the circulation system is provided with a discharge branch pipe.
Further, the synthesis reactor is of a vertical structure and comprises a fixed tube plate, and at least 2000 tubes are designed; wherein the tube side is filled with a catalyst and is used as a space for material synthesis reaction; the shell side is a heat exchange medium and is provided with a baffle plate.
Further, a heat exchanger is arranged on the pipeline at the front end of the synthesis reactor; and a heater is also arranged on a pipeline of the rectifying tower circulating system.
Further, regulating valves are arranged on the carbon monoxide pipeline and the methyl nitrite pipeline which are arranged behind the pressure swing adsorption equipment; valves are arranged on the discharge branch pipes of the circulating system and on the circulating system pipelines behind the discharge branch pipes.
Methyl nitrite is colorless and odorless gas at normal temperature and pressure, and has a melting point of-17 ℃ and a boiling point of-12 ℃ and a density d of 150.991g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Nitrous acid is easily released by hydrolysis, and is easily decomposed by heating, so that explosion is dangerous. Nitric oxide, oxygen and methanol react to form methyl nitrite. Carbon monoxide and Methyl Nitrite (MN) react under the condition of a catalyst to generate dimethyl oxalate; the invention utilizes carbon monoxide (CO) and sub-speciesMethyl Nitrate (MN) generates dimethyl carbonate (DMC) and Nitric Oxide (NO) under the action of a composite catalyst, and the product chain of an ethylene glycol device is prolonged through gas-phase oxidation hydroxylation of methanol, so that the dimethyl carbonate can be co-produced, wherein the chemical equation of the dimethyl carbonate synthesis principle is as follows:
CO+2MN→DMC+2NO。
1. the ethylene glycol device for co-producing the dimethyl carbonate is a good process route, raw materials of the ethylene glycol and the dimethyl carbonate are similar, and the loads of the two devices can be flexibly adjusted according to market or other requirements. And meanwhile, nitric Oxide (NO) generated in the production process of the dimethyl carbonate device can be returned to the ethylene glycol device for comprehensive recycling, so that the effects of energy saving and consumption reduction are obvious.
2. According to the invention, spinel-structure porous lithium aluminate is adopted as a carrier, 1-2wt% of palladium chloride, 3-15wt% of copper chloride and 0.1-0.2wt% of nanoscale cerium oxide are loaded as a composite catalyst, wherein the activity of palladium chloride is stable, and when the load capacity of palladium chloride is increased to 1-2wt%, the selectivity of synthesizing dimethyl carbonate by carbon monoxide (CO) and Methyl Nitrite (MN) is about 85.5%, but more byproducts of rearrangement reaction are generated, and more byproducts DMO, DME and the like are generated; the addition of the copper chloride can inhibit side reactions in the rearrangement reaction process, promote the consumption of palladium chloride oxidation reduction, and have synergistic effect when the ratio of palladium to copper is 1/3-1/10; further, by adding a small amount of nano-scale cerium oxide, the selectivity of the composite catalyst is more than or equal to 98.5%, the content of side reactant is reduced to 1.5%, the use of the composite catalyst can reduce the reaction temperature to 100-145 ℃, the pressure is reduced to below 0.3Mpa, and the industrial production device is more energy-saving.
3. The carrier in the composite catalyst adopts spinel structure porous lithium aluminate, and the reaction in the invention requires a certain temperature and pressure, but the inventor researches and discovers that the carrier must bear a certain pressure and have a certain compressive strength, otherwise, the carrier is easy to break and lose efficacy in the production process. The pressure and the reaction power exist in the synthetic reaction process of the dimethyl carbonate, and the catalyst must bear the compressive strength which is more than or equal to 25N. The spinel-structured porous lithium aluminate can only bear compressive strength less than 15N and is extremely easy to crush when being processed into spherical particles with the diameter less than or equal to 6mm, and the inventor can improve the compressive strength of the carrier by adding a small amount of polycarboxylic acid into the carrier in advance for pretreatment so as to meet the reaction requirement.
4. The addition of a small amount of hydrogen chloride in the synthesis reaction ensures that the catalyst maintains high activity for a long time, but the invention researches find that if the water content in the hydrogen chloride gas is large, the reactor is corroded and damaged, and the catalyst is further disabled; the inventor firstly dries the hydrogen chloride gas before introducing the hydrogen chloride gas, ensures that the moisture content is controlled to be less than or equal to 30ppm, can not corrode a reactor, and can realize long-term stable industrial production of DMC devices.
5. Regarding the synthesis reactor, the synthesis reactor adopts a fixed tube plate, is provided with at least 2000 tubes, passes through a Cheng Zhuangtian catalyst and is used as a space for material synthesis reaction; the shell side is designed with a flowing heat exchange medium which can be used for water, and a baffle plate is designed to ensure the flowing state of water and timely take away the heat generated in the synthesis reaction process. The vertical tube-array fixed tube plate type reactor is different from the conventional fixed bed reactor, so that the problem of heat aggregation in the synthesis exothermic reaction process can be effectively avoided, heat can be timely taken away, and the temperature balance and stability in the reaction process are ensured. In addition, as trace hydrogen chloride is added in the reaction, corrosion is easy to cause on equipment, the moisture in the hydrogen chloride gas is strictly controlled, meanwhile, the pressurized parts in the reactor are prepared from the duplex stainless steel, the corrosion problem can be solved, meanwhile, compared with other materials such as enamel, the single equipment can be large-sized, the productivity bottleneck is broken through, and the production capacity of the single equipment of the company where the inventor is located is more than 10 ten thousand tons/year.
Drawings
Fig. 1 is a schematic view of the structure of the apparatus provided by the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1:
a production process for co-producing dimethyl carbonate by a coal-to-ethylene glycol device comprises the following steps:
1) The ethylene glycol production device comprises a methyl nitrite production part, and can continuously provide Methyl Nitrite (MN) raw material;
2) The ethylene glycol production device also comprises a carbon monoxide production part by coal gasification, and the carbon monoxide is subjected to pressure swing adsorption to produce a high-purity carbon monoxide gas raw material with the purity of 99% -99.5%; mixing it with nitrogen; mixing with methyl nitrite, wherein the molar ratio of carbon monoxide to methyl nitrite is 2-3:1, the nitrogen accounts for more than 40 percent of the total gas volume;
3) Heating the gas obtained by mixing in the step 2) to 100-145 ℃ through a heat exchanger, adding a small amount of hydrogen chloride gas, wherein the hydrogen chloride is less than 200ppm, then sending the gas into a synthesis reactor to synthesize the dimethyl carbonate, carrying away a large amount of reaction heat through hot water flowing in a shell of a column tube along with exothermic reaction in the synthesis reaction process, controlling the reaction temperature of the reactor within the range of 100-145 ℃ and the pressure below 0.3Mpa, taking spinel-structured porous lithium aluminate as a carrier for a catalyst in the reactor, loading 1wt% of palladium chloride, 3wt% of copper chloride and 0.1wt% of nano cerium oxide, and discharging materials generated by the reaction from the bottom of the synthesis reactor.
4) The materials enter a separation rectifying tower and are subjected to gas-liquid separation rectification, wherein the gas materials mainly comprise Nitric Oxide (NO) and nitrogen (N) 2 ) Discharging from the top of the separation rectifying tower, and introducing into a methyl nitrite production part of an ethylene glycol production device for recycling; the liquid material dimethyl carbonate is discharged from the bottom of the separation rectifying tower, part of the material is conveyed to the refining process through a pump, and part of the material is conveyed back to the separation rectifying tower for recycling after being reheated by a heater, and the refining and recycling ratio is 20-40%, so that continuous operation is maintained.
In the embodiment, the selectivity of the combined catalyst is 98.7%, the catalyst keeps continuous long-term activity, the service life can reach more than 2 years, and the device can be ensured to continuously run for 2 years without stopping production. The purity of the refined dimethyl carbonate is 99.9-99.98 wt percent, and the yield can reach 99 percent.
Example 2:
in the production process of co-producing dimethyl carbonate by using a coal-to-ethylene glycol device, methyl nitrite from the ethylene glycol device and carbon monoxide from the ethylene glycol device are fully mixed under the nitrogen atmosphere, heat exchange is carried out to more than 100 ℃, then a small amount of hydrogen chloride gas is added, the volume concentration of the hydrogen chloride in the total gas is less than 200ppm, and the hydrogen chloride enters a synthesis reactor, and the pressure is controlled within the range of less than 0.3 Mpa; the temperature is controlled within the range of 100-145 ℃, and the synthesis reaction is carried out under the action of a combined catalyst of 2wt% of palladium chloride, 10wt% of copper chloride and 0.2wt% of nano-scale cerium oxide by taking spinel-structure porous lithium aluminate as a carrier.
After the synthesis reaction, the materials enter a separation rectifying tower, are subjected to gas-liquid separation rectification, and the gas materials containing Nitric Oxide (NO) are discharged from the top of the separation rectifying tower and are introduced into a methyl nitrite production part of an ethylene glycol production device for recycling; the liquid material dimethyl carbonate is discharged from the bottom of the separation rectifying tower, part of the material is conveyed to the refining process through a pump, and part of the material is conveyed back to the separation rectifying tower for recycling after being reheated by a heater, and the refining and recycling ratio is 20-40%, so that continuous operation is maintained.
The selectivity of the combined catalyst is more than 99%, the catalyst maintains continuous long-term activity, and the service life is more than 2 years.
Example 3:
in the production process of co-producing dimethyl carbonate by using a coal-to-ethylene glycol device, methyl nitrite from the ethylene glycol device and carbon monoxide from the ethylene glycol device are fully mixed under the nitrogen atmosphere, heat exchange is carried out to more than 100 ℃, then a small amount of hydrogen chloride gas is added, the volume concentration of the hydrogen chloride in the total gas is less than 200ppm, and the hydrogen chloride enters a synthesis reactor, and the pressure is controlled within the range of less than 0.3 Mpa; the temperature is controlled within the range of 100-145 ℃. Under the action of a composite catalyst of 1.5 weight percent of palladium chloride, 15 weight percent of copper chloride and 0.15 weight percent of nanoscale cerium oxide, which takes spinel-structured porous lithium aluminate as a carrier, a synthesis reaction occurs.
After the synthesis reaction, the materials enter a separation rectifying tower, are subjected to gas-liquid separation rectification, and the gas materials containing Nitric Oxide (NO) are discharged from the top of the separation rectifying tower and are introduced into a methyl nitrite production part of an ethylene glycol production device for recycling; the liquid material dimethyl carbonate is discharged from the bottom of the separation rectifying tower, part of the material is conveyed to the refining process through a pump, and part of the material is conveyed back to the separation rectifying tower for recycling after being reheated by a heater, and the refining and recycling ratio is 20-40%, so that continuous operation is maintained.
The selectivity of the combined catalyst is more than 98.7%, the catalyst maintains continuous long-term activity, and the service life is more than 2 years.
In the above examples 1 to 3, 5% of the polycarboxylic acid was added to the spinel-structured porous lithium aluminate before the composite catalyst was supported for pretreatment, and the service life of the treated catalyst was greatly prolonged by the pretreatment, for example, the catalyst was treated without adding the polycarboxylic acid, and the service life was 5 months or less.
Comparative example 1: wherein the catalyst used was 1.5wt% palladium chloride supported on spinel-structured porous lithium aluminate as a carrier, and the remainder was the same as in example 3. The catalyst selectivity was 85.5%.
Comparative example 2: the catalyst used therein was 1.5wt% palladium chloride and 15wt% copper chloride supported on spinel-structured porous lithium aluminate as a carrier, and the remainder was the same as in example 3. The selectivity of the catalyst was 98.5%.
Comparative example 3: the procedure of example 3 was repeated except that no hydrogen chloride gas was added before the mixed gas was introduced into the synthesis reactor. The selectivity of the catalyst is about 80%.
In the embodiment provided by the invention, the reaction pressure and the reaction temperature can be greatly reduced due to the cooperation of the technical characteristics, the equipment requirement and the investment are reduced, the energy consumption of a production device is reduced, the production cost can be greatly reduced, and the product profit is increased.
Example 4:
in the production process of the device for co-producing dimethyl carbonate by the device for producing ethylene glycol from coal, the synthesis reaction is as follows:
CO+2MN→DMC+2NO, this reaction is accompanied by the release of a large amount of heat. This part of the heat must be carried away in time or else the catalyst may fail. The synthesis reactor is core equipment, adopts a fixed tube plate, and designs 5000 tubes. Because the synthesis reaction is an organic reaction, and also a rearrangement reaction. The tube side is filled with a catalyst and is used as a space for material synthesis reaction; the shell side is provided with a flow heat exchange medium, namely water, and a baffle plate is designed to ensure the flow state of the water and timely take away the heat generated in the synthesis reaction process. Controlling the reaction temperature to be 100-130 ℃; the pressure was 0.3MPa. By adopting the equipment and the technological parameter control, the side reaction is successfully reduced, and the byproduct is less than 1.8 percent. The quality purity of the refined product can reach 99.98 percent; the device yield reaches 15 tons/hour and 12 ten thousand tons/year, the designed device has the highest world yield and annual yield, and the single annual yield of the similar device is only 3 ten thousand tons/year and 5 ten thousand tons/year.
During the synthesis reaction, the synthesis reactor is easy to corrode after the hydrogen chloride gas is added, and researches show that if the water content in the hydrogen chloride gas is controlled, the corrosion problem can be well solved by adopting the duplex stainless steel, and the corrosion effects of the duplex stainless steel material of UNS 32750 are greatly different under the action of the hydrogen chloride gas with different water contents as shown in the following table 1. Furthermore, the special bidirectional stainless steel and glass lining materials are adopted in the synthesis reactor and the rectifying tower by controlling the moisture content of the hydrogen chloride gas, so that the corrosion condition can be effectively prevented.
TABLE 1
Example 5:
as shown in fig. 1, a production device for co-producing dimethyl carbonate by a coal-to-ethylene glycol device comprises the coal-to-ethylene glycol device, wherein a methyl nitrite production system 1 and a coal gasification production carbon monoxide system 2 are arranged in the device, a carbon monoxide pipeline of the carbon monoxide system is connected with a methyl nitrite pipeline of the methyl nitrite production system after passing through pressure swing adsorption equipment and is introduced into a synthesis reactor 3, a discharge port of the synthesis reactor is connected to a feed port of a rectifying tower 4 through a pipeline, and a gas outlet at the top of the rectifying tower is connected to a gas inlet of the methyl nitrite production system 1; the rectifying tower is also provided with a circulating system, and a liquid outlet at the bottom of the rectifying tower is connected to a liquid return port of the circulating system through a pipeline and a pump 5; the circulation system is provided with a discharge branch 6.
Preferably, a heat exchanger 7 is also provided in the conduit at the front end of the synthesis reactor 3. And a heater 8 is also arranged on a pipeline of the rectifying tower circulation system.
Preferably, the synthesis reactor comprises a fixed tube plate, and at least 2000 tubes are designed for a vertical structure; wherein the tube side is filled with a catalyst and is used as a space for material synthesis reaction; the shell side is a heat exchange medium and is provided with a baffle plate.
Preferably, the carbon monoxide pipeline and the methyl nitrite pipeline behind the pressure swing adsorption equipment are respectively provided with a regulating valve. The regulating valve may be an automatically controlled regulating valve. Valves are arranged on the discharge branch pipes of the circulating system and on the circulating system pipelines behind the discharge branch pipes. In addition, in order to control the temperature conveniently, the synthesis reactor 3, the heat exchanger 7 and the heater 8 can be provided with temperature control systems, so that the automatic control of the systems is realized.
Claims (4)
1. The production process for co-producing dimethyl carbonate by using a coal-to-ethylene glycol device is characterized by comprising the following steps of:
1) The ethylene glycol device comprises a methyl nitrite production part and a carbon monoxide production part by coal gasification; carbon monoxide is mixed with methyl nitrite under nitrogen atmosphere after pressure swing adsorption, then preheating is carried out, a small amount of hydrogen chloride gas is added for mixing, the volume concentration of the hydrogen chloride gas is less than 200ppm, finally the mixed gas enters a reactor, the temperature is controlled to be 100-145 ℃, the pressure is less than or equal to 0.3Mpa, and the synthesis reaction of the dimethyl carbonate is carried out under the action of a composite catalyst; the composite catalyst takes spinel structure porous lithium aluminate as a carrier, 1-2wt% of palladium chloride, 3-15wt% of copper chloride and 0.1-0.2wt% of nano cerium oxide are loaded, and before the catalyst is loaded, 5% of polycarboxylic acid by mass of the spinel structure porous lithium aluminate is added and mixed uniformly;
2) And (2) feeding the materials after the synthesis reaction in the step (1) into a rectifying tower, carrying out gas-liquid separation through rectification at the temperature of 120-180 ℃, directly discharging the gas after rectification treatment containing nitric oxide, and leading the liquid after rectification out to a refining process for refining to obtain the dimethyl carbonate.
2. The production process according to claim 1, characterized in that: the purity of the carbon monoxide after pressure swing adsorption is 99.0-99.5%, and the molar ratio of the carbon monoxide to the methyl nitrite is 1.7-2.5: 0.8-1.1; the nitrogen accounts for more than 40 percent of the total volume of the carbon monoxide and the methyl nitrite.
3. The production process according to claim 1, characterized in that: the water content in the hydrogen chloride gas is less than or equal to 30ppm.
4. The production process according to claim 1, characterized in that: the exhausted gas in the step 2) contains nitric oxide and is introduced into a methyl nitrite production part of an ethylene glycol production device for recycling; part of the liquid separated by rectification is sent to the subsequent refining process, and the other part is heated and then enters the rectification process again for recycling.
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| CN1104205A (en) * | 1993-07-15 | 1995-06-28 | 拜尔公司 | Process for the preparation of dimethyl cxarbonate |
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| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| CN103977813A (en) * | 2014-04-24 | 2014-08-13 | 华东师范大学 | Integrally-used palladium catalyst, preparation method and application thereof |
| CN111085220A (en) * | 2019-12-27 | 2020-05-01 | 宁波中科远东催化工程技术有限公司 | Catalyst, preparation method thereof and dimethyl carbonate synthesis method |
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| CN1104205A (en) * | 1993-07-15 | 1995-06-28 | 拜尔公司 | Process for the preparation of dimethyl cxarbonate |
| US5514829A (en) * | 1993-11-26 | 1996-05-07 | Ube Industries, Ltd. | Process for continuously producing dimethyl carbonate |
| CN1147424A (en) * | 1995-05-22 | 1997-04-16 | 宇部兴产株式会社 | Porous lithium aluminate carrier of spinel structure for catalyst |
| JPH0912512A (en) * | 1995-06-28 | 1997-01-14 | Ube Ind Ltd | Production of carbonate diester |
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