CN111606805A - 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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- CN111606805A CN111606805A CN202010387512.3A CN202010387512A CN111606805A CN 111606805 A CN111606805 A CN 111606805A CN 202010387512 A CN202010387512 A CN 202010387512A CN 111606805 A CN111606805 A CN 111606805A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 39
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000007670 refining Methods 0.000 claims abstract description 10
- 239000003245 coal Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 7
- 238000002309 gasification Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 27
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 239000011029 spinel Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229940093476 ethylene glycol Drugs 0.000 claims 8
- 238000000926 separation method Methods 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative 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
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- 238000007086 side reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 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
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product 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
- 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
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- 230000009965 odorless effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
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- 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
- 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
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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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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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
- 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
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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 through coal gasification; mixing carbon monoxide with methyl nitrite, controlling the temperature at 100-145 ℃ and the pressure at less than or equal to 0.3Mpa, and carrying out the synthesis reaction of dimethyl carbonate under the action of the composite catalyst; and (3) carrying out gas-liquid separation and rectification on the reacted material, directly discharging the nitric oxide contained in the separated gas, and leading the rectified liquid to a refining process for refining to obtain the dimethyl carbonate. The process can realize the 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 added; meanwhile, a byproduct nitric oxide generated in the production process of the dimethyl carbonate device can be returned to the ethylene glycol device, the 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 device for preparing ethylene glycol from coal gasifies to produce carbon monoxide, and a large amount of high-purity carbon monoxide gas raw material is generated after pressure swing adsorption; methyl nitrite, which is a raw material for producing ethylene glycol, is synthesized from methanol, oxygen and Nitric Oxide (NO) before ethylene glycol synthesis. To adapt to market changes, keeping the device safe and stable for long term operation at end of load, and extending the product chain is a sound solution.
CN101462961A discloses a process flow for producing ethylene glycol and co-producing dimethyl carbonate, which is a linked process for synthesizing ethylene glycol and co-producing dimethyl carbonate by using carbon monoxide and methyl nitrite as initial raw materials. But actually, it is a by-product dimethyl carbonate for ethylene glycol equipment, and the ethylene glycol equipment itself is a by-product dimethyl carbonate, and the main product proportion is 33.6 wt% of dimethyl oxalate, 17.9 wt% of dimethyl carbonate and 48.1 wt% of methanol, and the formation of the dimethyl carbonate is a gas phase oxidative coupling reaction, and the catalyst used in the reaction has poor selectivity, and the yield and purity of dimethyl carbonate are low.
Disclosure of Invention
The invention provides a production process and a device for co-producing dimethyl carbonate by a coal-to-ethylene glycol device, wherein the dimethyl carbonate can safely and stably run at the end of a long period; the product chain in the production of ethylene glycol is prolonged, and the dimethyl carbonate product is added; the device system is energy-saving and consumption-reducing.
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 through coal gasification; after pressure swing adsorption, mixing carbon monoxide with methyl nitrite in a nitrogen atmosphere, then preheating, adding a small amount of hydrogen chloride gas for mixing, wherein the volume concentration of the hydrogen chloride gas is less than 200ppm, finally, feeding the mixed gas into a reactor, controlling the temperature to be 100 ℃ and the pressure to be less than or equal to 0.3Mpa, and carrying out a dimethyl carbonate synthesis reaction under the action of a composite catalyst;
2) and (2) feeding the material obtained after the synthetic reaction in the step 1) into a rectifying tower at the temperature of 120-.
Further, the purity of the carbon monoxide subjected to pressure swing adsorption is 99.0-99.5%, and the molar ratio of the carbon monoxide to methyl nitrite is 1.7-2.5: 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.
Furthermore, the water content in the hydrogen chloride gas is less than or equal to 30 ppm.
Further, the composite catalyst in the step 1) takes porous lithium aluminate with a spinel structure as a carrier, and 1-2wt% of palladium chloride, 3-15wt% of copper chloride and 0.1-0.2wt% of nano cerium oxide are loaded.
Furthermore, the spinel-structured porous lithium aluminate is added with 5 percent of polycarboxylic acid by mass and mixed evenly before the catalyst is loaded.
Further, the exhaust gas in the step 2) contains nitric oxide, and is introduced into a methyl nitrite production part of the ethylene glycol production device for recycling; and (4) sending part of the liquid separated by rectification to a subsequent refining process, and heating part of the liquid and then entering the rectification process again for recycling.
The invention also relates to a production device for co-producing dimethyl carbonate by the coal-to-ethylene glycol device, which comprises the coal-to-ethylene glycol device, wherein a methyl nitrite production system and a carbon monoxide production system for coal gasification 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 a pressure swing adsorption device 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 circulating 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.
Furthermore, a heat exchanger is also arranged on a pipeline at the front end of the synthesis reactor; and a heater is also arranged on the pipeline of the rectifying tower circulating system.
Furthermore, regulating valves are respectively arranged on the carbon monoxide pipeline and the methyl nitrite pipeline behind the pressure swing adsorption equipment; valves are arranged on the discharge branch pipe of the circulating system and the circulating system pipeline behind the discharge branch pipe.
Methyl nitrite is a colorless and odorless gas at normal temperature and pressure, and has melting point of-17 deg.C, boiling point of-12 deg.C, and density of d150.991g/cm3(ii) a It is easy to hydrolyze to release nitrous acid, and is easy to decompose when heated, so that the danger of explosion is generated. Nitric oxide + oxygen + methanol to produce methyl nitrite. Reacting carbon monoxide and Methyl Nitrite (MN) under the condition of a catalyst to generate dimethyl oxalate; the invention utilizes the principle that carbon monoxide (CO) and Methyl Nitrite (MN) generate dimethyl carbonate (DMC) and Nitric Oxide (NO) under the action of a composite catalyst, prolongs the product chain of an ethylene glycol device through methanol gas phase oxidation hydroxylation, and can CO-produce dimethyl carbonate, wherein the chemical equation of the dimethyl carbonate synthesis principle is as follows:
CO+2MN→DMC+2NO。
1. the ethylene glycol device co-production of dimethyl carbonate provided by the invention is a good process route, the raw materials of ethylene glycol and dimethyl carbonate are similar, and the loads of the two devices can be flexibly adjusted according to market or other requirements. 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, and the effects of energy conservation and consumption reduction are obvious.
2. According to the invention, porous lithium aluminate with a spinel structure is used as a carrier, and 1-2wt% of palladium chloride, 3-15wt% of copper chloride and 0.1-0.2wt% of nano cerium oxide are loaded as a composite catalyst, wherein the palladium chloride has stable activity, when the loading capacity of the palladium chloride is increased to 1-2wt%, the selectivity of synthesizing dimethyl carbonate by using carbon monoxide (CO) and Methyl Nitrite (MN) is about 85.5%, but the number of rearrangement reaction byproducts is large, and more byproducts DMO and DME are generated; the addition of copper chloride can inhibit side reactions in the rearrangement reaction process and promote the consumption of palladium chloride by oxidation reduction, and the palladium and the copper have a synergistic effect when the ratio of the palladium to the copper is 1/3-1/10; furthermore, the addition of a small amount of nano-scale cerium oxide can ensure that the selectivity of the composite catalyst is more than or equal to 98.5 percent, the side reaction products are reduced to 1.5 percent, the use of the composite catalyst can reduce the reaction temperature to 100-145 ℃, the pressure to below 0.3Mpa, and the industrial production device is more energy-saving.
3. The carrier in the composite catalyst adopts porous lithium aluminate with a spinel structure, and the reaction in the invention needs certain temperature and pressure, but the inventor researches and finds that the carrier can bear certain pressure and has certain compressive strength, otherwise, the carrier is easy to lose efficacy due to carrier breakage in the production process. The pressure and reaction power exist in the process of synthesizing dimethyl carbonate, and the catalyst must bear the compressive strength of more than or equal to 25N. When the porous lithium aluminate with the spinel structure is processed into spherical particles with the diameter less than or equal to 6mm, the porous lithium aluminate can only bear the compressive strength less than 15N and is easy to break, and the inventor adds a small amount of polycarboxylic acid into the carrier in advance for pretreatment, so that the compressive strength of the carrier can be improved, and the carrier meets the reaction requirement.
4. A small amount of hydrogen chloride is added in the synthesis reaction to ensure that the catalyst can keep high activity for a long time, but the research of the invention finds that if the water content in the hydrogen chloride gas is higher, the hydrogen chloride gas causes corrosion damage to the reactor, and further causes the catalyst to lose efficacy; the inventor dries the hydrogen chloride gas before introducing the hydrogen chloride gas to ensure that the water content is controlled to be less than or equal to 30ppm, so that the corrosion to a reactor can be avoided, and the long-term stable industrial production of the DMC device can be realized.
5. Regarding the synthesis reactor, the synthesis reactor adopts a fixed tube plate, at least 2000 tubes are designed, and the fixed tube plate is filled with a catalyst in the process and is used as a space for material synthesis reaction; the shell side is designed with a flowing heat exchange medium which can be water, and the baffle plate is designed to ensure the flowing state of water and take away heat generated in the synthesis reaction process in time. The vertical tube-fixed plate reactor with the tubes is different from a conventional fixed bed reactor, so that the problem of heat accumulation in the synthesis exothermic reaction process can be effectively avoided, heat can be taken away in time, and the temperature balance and stability in the reaction process can be ensured. In addition, because trace hydrogen chloride is added in the reaction, the equipment is easy to corrode, the water content in the hydrogen chloride gas is strictly controlled, parts under pressure in the reactor are prepared from duplex stainless steel, the corrosion problem can be solved, and meanwhile, compared with other parts adopting enamel and other materials, a single set of equipment can be large-sized, the capacity bottleneck is broken through, and the production capacity of a single set of equipment of a company of an inventor is more than 10 ten thousand tons per year.
Drawings
FIG. 1 is a schematic view of the structure of the apparatus of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of 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 a Methyl Nitrite (MN) raw material;
2) the ethylene glycol production device also comprises a carbon monoxide part produced 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; and mixing with methyl nitrite, wherein the molar ratio of carbon monoxide to methyl nitrite is 2-3: 1, nitrogen accounts for more than 40% 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 gas is less than 200ppm, then sending the hydrogen chloride gas into a synthesis reactor to synthesize dimethyl carbonate, wherein the synthesis reaction process is accompanied with an exothermic reaction, a large amount of reaction heat is taken away by hot water flowing in a shell of a tube array, the reaction temperature of the reactor is controlled within the range of 100-145 ℃, the pressure is controlled below 0.3Mpa, a catalyst in the reactor takes porous lithium aluminate with a spinel structure as a carrier, 1 wt% of palladium chloride, 3 wt% of copper chloride and 0.1 wt% of nano cerium oxide are loaded, and the material generated by the reaction is discharged from the bottom of the synthesis reactor.
4) The material enters a separation rectifying tower and is subjected to gas-liquid separation and rectification, and the gas material mainly comprises Nitric Oxide (NO) and nitrogen (N)2) Discharging from the top of the separation and rectification 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 a refining process through a pump, part of the material is reheated by a heater and then conveyed back to the separation rectifying tower for recycling, the refining and recycling proportion is 20-40%, and 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 of the catalyst can reach more than 2 years, and the continuous operation of the device for 2 years without stopping production is ensured. The purity of the refined dimethyl carbonate is 99.9 wt% -99.98 wt%, and the yield can reach 99%.
Example 2:
in the production process of coproducing 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 over 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, the hydrogen chloride gas 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 composite catalyst which takes porous lithium aluminate with a spinel structure as a carrier, and loads 2wt% of palladium chloride, 10 wt% of copper chloride and 0.2wt% of nano cerium oxide.
After the synthesis reaction, the material enters a separation rectifying tower, and is subjected to gas-liquid separation rectification, wherein the gas material containing Nitric Oxide (NO) is discharged from the top of the separation rectifying tower and is 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 a refining process through a pump, part of the material is reheated by a heater and then conveyed back to the separation rectifying tower for recycling, the refining and recycling proportion is 20-40%, and continuous operation is maintained.
The selectivity of the combined catalyst is more than 99 percent, the catalyst keeps continuous long-term activity, and the service life is more than 2 years.
Example 3:
in the production process of coproducing 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 over 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, the hydrogen chloride gas 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 catalyst composition which takes porous lithium aluminate with a spinel structure as a carrier and loads 1.5 wt% of palladium chloride, 15wt% of copper chloride and 0.15 wt% of nano cerium oxide, a synthetic reaction occurs.
After the synthesis reaction, the material enters a separation rectifying tower, and is subjected to gas-liquid separation rectification, wherein the gas material containing Nitric Oxide (NO) is discharged from the top of the separation rectifying tower and is 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 a refining process through a pump, part of the material is reheated by a heater and then conveyed back to the separation rectifying tower for recycling, the refining and recycling proportion is 20-40%, and continuous operation is maintained.
The selectivity of the combined catalyst is more than 98.7 percent, the catalyst keeps continuous long-term activity, and the service life is more than 2 years.
In examples 1 to 3, the porous lithium aluminate having a spinel structure was pretreated with 5% of polycarboxylic acid before the composite catalyst was supported, and the service life of the treated catalyst was significantly prolonged, but the service life was 5 months or less without the polycarboxylic acid.
Comparative example 1: wherein the catalyst used was the same as in example 3 except that a porous lithium aluminate having a spinel structure was used as a carrier and 1.5 wt% of palladium chloride was supported. The catalyst selectivity was 85.5%.
Comparative example 2: wherein the catalyst used was the same as in example 3 except that a porous lithium aluminate having a spinel structure was used as a carrier and 1.5% by weight of palladium chloride and 15% by weight of copper chloride were supported. The catalyst selectivity was 98.5%.
Comparative example 3: the same procedure as in example 3 was repeated except that no hydrogen chloride gas was added to the mixed gas before the mixed gas was introduced into the synthesis reactor. The selectivity of the catalyst is about 80 percent.
In the embodiment provided by the invention, due to the matching of all technical characteristics, the reaction pressure and the reaction temperature can be greatly reduced, 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 a production process of a device for co-producing dimethyl carbonate by a coal glycol device, the synthesis reaction is as follows:
CO +2MN → DMC +2NO, with the release of a large amount of heat. This portion of the heat must be removed in a timely manner or it can cause catalyst failure. The synthesis reactor is a core device, adopts a fixed tube plate, and is designed with 5000 rows of tubes. Since the synthesis reaction is an organic reaction, it is also a rearrangement reaction. Filling a catalyst in the tube pass to serve as a space for material synthesis reaction; the shell side is filled with flowing heat exchange medium-water, and baffle plates are designed to ensure the flowing state of water and take away the heat generated in the synthesis reaction process in time. Controlling the reaction temperature to be 100-130 ℃; the pressure is 0.3 MPa. By adopting the equipment and the process parameter control, the side reaction is successfully reduced, and the by-product is less than 1.8 percent. The quality and purity of the refined product can reach 99.98 percent; the output of the device reaches 15 tons/hour and 12 ten thousand tons/year, the hourly output and the annual output of the designed device are the highest level in the world, and the annual output of a single set of devices of the same type is only 3 ten thousand tons/year and 5 ten thousand tons/year at present.
During the synthesis reaction, the synthesis reactor is easily corroded after 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, as shown in the following table 1, the corrosion effect of the duplex stainless steel material UNSS32750 is greatly different under the action of the hydrogen chloride gas with different water contents. Furthermore, by controlling the moisture content of the hydrogen chloride gas and adopting special bidirectional stainless steel and glass lining materials for the synthesis reactor and the rectifying tower, the corrosion 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 the device is provided with a methyl nitrite production system 1 and a carbon monoxide production system 2 for producing carbon monoxide by coal gasification, a carbon monoxide pipeline of the carbon monoxide production system is connected with a methyl nitrite pipeline of the methyl nitrite production system after passing through a pressure swing adsorption device 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, the front end of the synthesis reactor 3 is also provided with a heat exchanger 7 on the pipeline. And a heater 8 is also arranged on the pipeline of the rectifying tower circulating system.
Preferably, the synthesis reactor comprises a fixed tube plate, is of a vertical structure and is provided with at least 2000 tubes; 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 both provided with regulating valves. The regulating valve may be an automatically controlled regulating valve. Valves are arranged on the discharge branch pipe of the circulating system and the circulating system pipeline behind the discharge branch pipe. In addition, in order to control the temperature conveniently, a temperature control system can be arranged on the synthesis reactor 3, the heat exchanger 7 and the heater 8, so that the automatic control of the system is realized.
Claims (10)
1. A production process for co-producing dimethyl carbonate by a coal-to-ethylene glycol device is characterized by comprising the following steps:
1) the ethylene glycol device comprises a methyl nitrite production part and a carbon monoxide production part through coal gasification; after pressure swing adsorption, mixing carbon monoxide with methyl nitrite in a nitrogen atmosphere, then preheating, adding a small amount of hydrogen chloride gas for mixing, wherein the volume concentration of the hydrogen chloride gas is less than 200ppm, finally, feeding the mixed gas into a reactor, controlling the temperature to be 100 ℃ and the pressure to be less than or equal to 0.3Mpa, and carrying out a dimethyl carbonate synthesis reaction under the action of a composite catalyst;
2) and (2) feeding the material obtained after the synthetic reaction in the step 1) into a rectifying tower at the temperature of 120-.
2. The production process according to claim 1, characterized in that: the purity of the carbon monoxide subjected to pressure swing adsorption is 99.0-99.5%, and the molar ratio of the carbon monoxide to methyl nitrite is 1.7-2.5: 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.
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 30 ppm.
4. The production process according to claim 1, characterized in that: the composite catalyst in the step 1) takes porous lithium aluminate with a spinel structure as a carrier, and 1-2wt% of palladium chloride, 3-15wt% of copper chloride and 0.1-0.2wt% of nano cerium oxide are loaded.
5. The production process according to claim 4, characterized in that: adding polycarboxylic acid accounting for 5% of the mass of the spinel-structured porous lithium aluminate before loading the catalyst, and uniformly mixing.
6. The production process according to claim 1, characterized in that: introducing the nitric oxide-containing exhaust gas containing nitric oxide into a methyl nitrite production part of an ethylene glycol production device for recycling; and (4) sending part of the liquid separated by rectification to a subsequent refining process, and heating part of the liquid and then entering the rectification process again for recycling.
7. A production device for co-producing dimethyl carbonate by a coal-to-ethylene glycol device is characterized by comprising the coal-to-ethylene glycol device, wherein the device is internally provided with a methyl nitrite production system (1) and a carbon monoxide production system (2) for coal gasification, a carbon monoxide pipeline of the carbon monoxide production system is connected with a methyl nitrite pipeline of the methyl nitrite production system after passing through a pressure swing adsorption device 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 upper part of the rectifying tower (4) 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 circulating system is provided with a discharge branch pipe (6).
8. The production device for coproducing dimethyl carbonate by the coal-to-ethylene-glycol plant according to claim 7, which is characterized in that: the synthesis reactor is of a vertical structure, comprises a fixed tube plate and is provided with at least 2000 tubes; 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.
9. The production device for coproducing dimethyl carbonate by the coal-to-ethylene-glycol plant according to claim 7, which is characterized in that: a heat exchanger (7) is also arranged on the pipeline at the front end of the synthesis reactor; and a heater (8) is also arranged on the pipeline of the rectifying tower circulating system.
10. The production device for coproducing dimethyl carbonate by the coal-to-ethylene-glycol plant according to claim 7, which is characterized in that: the carbon monoxide pipeline and the methyl nitrite pipeline behind the pressure swing adsorption equipment are both provided with regulating valves; valves are arranged on the discharge branch pipe of the circulating system and the circulating system pipeline behind the discharge branch pipe.
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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 |
| 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 |
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