CN104803832A - MTBE (methyl tert-butyl ether) production system - Google Patents
MTBE (methyl tert-butyl ether) production system Download PDFInfo
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- CN104803832A CN104803832A CN201510129091.3A CN201510129091A CN104803832A CN 104803832 A CN104803832 A CN 104803832A CN 201510129091 A CN201510129091 A CN 201510129091A CN 104803832 A CN104803832 A CN 104803832A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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Abstract
The invention provides an MTBE (methyl tert-butyl ether) production system. The MTBE production system comprises a methyl alcohol supply part, a coal-based C4 supply part, a hydrogen supply part, an MTBE reaction tank, a hydrogenation reaction assembly and a dehydrogenation tower assembly, wherein a methyl alcohol feeding port, an isobutene feeding port and an MTBE reactant discharging port are formed in the MTBE reaction tank, and the methyl alcohol feeding port is connected with the methyl alcohol supply part; a coal-based C4 feeding port, a hydrogen feeding port and a hydrogenation material outlet are formed in the hydrogenation reaction assembly, the coal-based C4 feeding port and the coal-based C4 supply part are connected, and the hydrogen feeding port and the hydrogen supply part are connected; a to-be-dehydrogenized material inlet and a heavy material outlet are formed in the dehydrogenation tower assembly, the to-be-dehydrogenized material inlet is connected with the hydrogenation material outlet, and the heavy material outlet is connected with the isobutene feeding port. According to the MTBE production system, the process route of impurity removal and later reaction is realized, the generation of high-molecular polymers is avoided, so that the problem that the activity of a catalyst is reduced due to generation of the high-molecular polymers is solved, and the MTBE product quality is improved.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of MTBE production system
Background technology
Ethene, propylene are one of most important Chemicals in the world today, and it is mainly produced by petroleum cracking, and this just causes a large amount of consumption of oil.DMTO is the technology doing raw materials for ethylene production and propylene with coal or substitute gas oil.For the China of product big country, with DMTO technology produce ethene and propylene than oil be raw material have more the market competitiveness.DMTO industrialization technology is researched and developed successfully, and for minimizing China's oil entrance, to open up China's alkene industry new way significant.Also indicate that China's methyl alcohol working ability will cross megaton large-scale plant at one stroke by ton device simultaneously.
Preparing in the process of ethene and propylene above-mentioned, be attended by the generation of byproduct coal-based carbon 4 mixture simultaneously, in order to improve the comprehensive utilization ratio of mixed c 4, in prior art, utilizing the coal-based carbon 4 mixture of by-product to prepare MTBE product.But, the MTBE product prepared by the coal-based carbon 4 mixture of by-product in actual production process fails to reach the market demands as gasoline blender always, this is mainly because of dipolymer, trimeric content overproof in MTBE product, two, trimeric total content is between 6 ~ 8%, cause the content of MTBE and effective constituent (the MSBE+ trimethyl carbinol) thereof on the low side, product is faint yellow, belongs to unacceptable product, affects the sale of product.MTBE: methyl tertiary butyl ether, MSBE: methyl sec-butyl ether are the reaction product of 1-butylene and methyl alcohol.
And dipolymer in MT reconnaissance BE product, trimeric content overproof is mainly because 1 in coal-based carbon 4 mixture, the too high levels of 3 divinyl and the existence of a small amount of unsaturated olefin, and 1, 3 divinyl and a small amount of unsaturated hydrocarbons (2-methyl butene-1 existed, 2-methyl butene-2 etc.) very easily there is self-polymeric reaction, reaction generates dipolymer or trimer, this high molecular polymer can part can be adsorbed in catalyst for etherification bed, part enters in MTBE product, the polymkeric substance being adsorbed on beds can affect the activity of catalyzer, final efficiency and the catalyst life affecting catalyzer.The high molecular polymer entering MTBE product just directly affects quality product, and along with the start-stop car of device, the high molecular polymer being adsorbed on beds also can drop in MTBE product, cause dipolymer in the finished product MTBE, trimeric content overproof, do not reach product requirement standard.
Based on the problems referred to above, be necessary to propose a kind of effective means, to reduce dipolymer and trimeric content in MTBE, and then improve the quality of MTBE product, reach product requirement standard.
Summary of the invention
The present invention aims to provide a kind of MTBE production system, to reduce dipolymer and trimeric content in MTBE.
To achieve these goals, according to an aspect of the present invention, provide a kind of MTBE production system, this MTBE production system comprises: methyl alcohol supply department; Coal-based carbon four supply department; Hydrogen supplying portion; MTBE retort, which is provided with methyl alcohol feeding mouth, iso-butylene feeding mouth and MTBE reactant discharge port, methyl alcohol feeding mouth is connected with methyl alcohol supply department; Hydrogenation reaction assembly, which is provided with coal-based carbon four feeding mouth and hydrogen feeding mouth, and hydrogenation material outlet, and coal-based carbon four feeding mouth is connected with coal-based carbon four supply department, and hydrogen feeding mouth is connected with hydrogen supplying portion; Dehydrogenation tower assembly, which is provided with and treat dehydrogenation material inlet and heavier feeds outlet, treat that dehydrogenation material inlet is connected with hydrogenation material outlet, heavier feeds outlet is connected with iso-butylene feeding mouth.
Further, above-mentionedly treat that the connection line between dehydrogenation material inlet and hydrogenation material outlet is provided with outer row's material mouth, outer row's material mouth is connected with external heavy carbon four tank.
Further, above-mentioned hydrogenation reaction assembly comprises: the first hydrogenation reaction tank, and coal-based carbon four feeding mouth and hydrogen feeding mouth are positioned on the first hydrogenation reaction tank; Second hydrogenation reaction tank, is positioned at the downstream of the first hydrogenation reaction tank, and hydrogenation material outlet is positioned on the second hydrogenation reaction tank; First Heat Exchanger, is connected between the first hydrogenation reaction tank and the second hydrogenation reaction tank.
Further, above-mentioned dehydrogenation tower assembly comprises: dehydrogenation tower body, which is provided with and treat dehydrogenation material inlet and heavier feeds outlet, and gas light material exports and light recycle material inlet; First circulation tank, which is provided with gas light material entrance, light recycle material outlet and fuel gas outlet; Gas light material entrance is connected with gas lightweight thing discharge port, and light recycle material outlet is connected with light recycle material inlet; Second interchanger, be arranged on gas light material entrance and gas light material export between stream on.
Further, MT reconnaissance BE reactive system also comprises removal of impurities separation system, and removal of impurities separation system is connected with the MTBE reactant discharge port of MTBE retort, comprises the MTBE separation assembly, separating methanol assembly and the C that sequentially arrange
4separation assembly.
Further, MT reconnaissance BE separation assembly comprises: tower under catalytic distillation, under catalytic distillation tower sidewall on be provided with first and treat catalytic distillation thing entrance and circulation catalysis material inlet, under catalytic distillation, the top of tower is provided with the first gaseous mixture outlet, and under catalytic distillation, tower bottom is provided with MTBE outlet; Tower on catalytic distillation, on catalytic distillation tower sidewall on be provided with second and treat catalytic distillation thing entrance, on catalytic distillation, top of tower is provided with the second gaseous mixture outlet, and on catalytic distillation, tower bottom is provided with circulation catalysis material outlet; Second treats that catalytic distillation thing entrance exports with the first gaseous mixture is connected, and circulation catalysis material outlet is connected with circulation catalysis material inlet, and the second gaseous mixture outlet is connected with follow-up separating methanol assembly.
Further, MT reconnaissance BE separation assembly also comprises: the second circulation tank, which is provided with gaseous mixture entrance and the outlet of the 3rd gaseous mixture, the 3rd gaseous mixture outlet is connected with the circulation gas entrance be arranged on catalytic distillation on tower and follow-up separating methanol assembly respectively; 3rd interchanger, is arranged between the second gaseous mixture outlet and gas mixture entrance.
Further, above-mentioned separating methanol assembly comprises: dissolve with methanol tank, and the sidewall of dissolve with methanol tank is provided with methyl alcohol/C
4entrance and recirculated water entrance, top is provided with C
4outlet, bottom is provided with methanol-water outlet, and recirculated water entrance is positioned at methyl alcohol/C
4entrance and C
4between outlet; Methanol extraction tank, the sidewall of methanol extraction tank is provided with methanol-water entrance and self-circulating water entrance, top is provided with methanol charge outlet, and bottom is provided with circulating water outlet and self-circulating water outlet, is provided with the 4th interchanger between self-circulating water outlet and self-circulating water entrance; Methanol-water outlet is connected with methanol-water entrance, and circulating water outlet is connected with recirculated water entrance, C
4the C in outlet and downstream
4separation assembly is connected, and methanol charge outlet is connected with Methanol Recovery tank.
Further, above-mentioned separating methanol assembly comprises: the 5th interchanger, is arranged between methanol-water outlet and methanol-water entrance, and communicates with circulating water outlet and recirculated water entrance.
Further, above-mentioned C
4separation system comprises: debutanizing tower, and its upper side wall is provided with C
4entrance, bottom is provided with debutylize outlet, top is provided with the first heavy C
4outlet; Butene-1 rectifying tower, its upper side wall arranges and needs that rectifying entrance, top are provided with butene-1 outlet, bottom is provided with the second heavy C
4outlet; C
4entrance is connected with the separating methanol assembly of upstream, and debutylize exports and treats that rectifying entrance is connected.
Apply a kind of MTBE production system of technical scheme of the present invention, by coal-based carbon four supply department is connected with hydrogenation reaction assembly, enters MTBE retort again after flowing through hydrogenating component and dehydrogenation tower assembly and carry out etherification reaction.This MTBE production system in use, coal-based carbon 4 mixture is joined together with hydrogen in hydrogenation reaction assembly, make 1 in coal-based carbon 4 mixture, 3 divinyl and carbon five unsaturated hydrocarbons that some are a small amount of, such as, there is hydrogenation reaction with hydrogen and generate butane and other alkyl in 2-methyl butene-1,2-methyl butene-2 or other alkene in hydrogenating component, thus 1,3 divinyl removed in coal-based carbon 4 mixture and a small amount of carbon five unsaturated hydrocarbons.Again the coal-based carbon four after hydrogenation removing impurities is added to after dehydrogenation tower assembly Dehydroepiandrosterone derivative together with methyl alcohol MTBE retort and carries out etherification reaction generation MTBE product.
Such MTBE production system achieves the post-reacted operational path of first removal of impurities, avoid 1,3 divinyl and a small amount of unsaturated hydrocarbons existed, such as, there is self-polymeric reaction in 2-methyl butene-1 and 2-methyl butene-2, generate the phenomenon of high molecular polymer, thus high molecular polymer can not occur be adsorbed in catalyst for etherification bed, cause the problem that the activity of catalyzer reduces, and then improve MTBE reaction efficiency; Reduce and occur that superpolymer infiltrates the probability of the phenomenon in MTBE product, finally improve the quality of MTBE product, meet the requirement of Process Design Package standard, there is good economic benefit.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic flow sheet of the MTBE system according to the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing of embodiment of the present invention, be described in detail, it should be noted that the technical scheme in embodiments of the invention, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
Introduce as background technology part, in prior art, there is dipolymer in MTBE, trimeric content overproof, fail to reach the problem of Process Design Package requirement standard always.In order to address this problem, inventor provides a kind of MTBE production system.As shown in Figure 1, this MTBE production system comprises methyl alcohol supply department 10, coal-based carbon four supply department 20, hydrogen supplying portion 30, MTBE retort 40, hydrogenation reaction assembly and dehydrogenation tower assembly.Wherein, MTBE retort 40 is provided with methyl alcohol feeding mouth, iso-butylene feeding mouth and MTBE reactant discharge port, and methyl alcohol feeding mouth is connected with methyl alcohol supply department 10.Hydrogenation reaction assembly is provided with coal-based carbon four feeding mouth and hydrogen feeding mouth, and hydrogenation material outlet, and coal-based carbon four feeding mouth is connected with coal-based carbon four supply department 20, and hydrogen feeding mouth is connected with hydrogen supplying portion 30.And dehydrogenation tower assembly be provided with treat dehydrogenation material inlet and heavier feeds outlet, treat that dehydrogenation material inlet is connected with hydrogenation material outlet, heavier feeds export be connected with iso-butylene feeding mouth.
MT reconnaissance BE production system of the present invention, by coal-based carbon four supply department being connected with hydrogenation reaction assembly, entering MTBE retort again after flowing through hydrogenating component and dehydrogenation tower assembly and carrying out etherification reaction.This MTBE production system in use, coal-based carbon 4 mixture is joined together with hydrogen in hydrogenation reaction assembly, make 1 in coal-based carbon 4 mixture, 3 divinyl and carbon five unsaturated hydrocarbons that some are a small amount of, such as, there is hydrogenation reaction with hydrogen and generate butane and other alkyl in 2-methyl butene-1,2-methyl butene-2 or other alkene in hydrogenating component, thus 1,3 divinyl removed in coal-based carbon 4 mixture and a small amount of carbon five unsaturated hydrocarbons.Again the coal-based carbon four after hydrogenation removing impurities is added to after dehydrogenation tower assembly Dehydroepiandrosterone derivative together with methyl alcohol MTBE retort and carries out etherification reaction generation MTBE product.
Such MTBE production system achieves the post-reacted operational path of first removal of impurities, avoid 1,3 divinyl and a small amount of unsaturated hydrocarbons existed, such as, there is self-polymeric reaction in 2-methyl butene-1 and 2-methyl butene-2, generate the phenomenon of high molecular polymer, thus high molecular polymer can not occur be adsorbed in catalyst for etherification bed, cause the problem that the activity of catalyzer reduces, and then improve MTBE reaction efficiency; Reduce and occur that superpolymer infiltrates the probability of the phenomenon in MTBE product, finally improve the quality of MTBE product, meet the requirement of Process Design Package standard, there is good economic benefit.
In actually operating, in MT reconnaissance BE production system, the outlet of connection heavier feeds and coal-based carbon four pipeline of iso-butylene feeding mouth can also be disposed with at least one interchanger and at least one well heater, the interchanger of coal-based carbon four first process carries out heat exchange cooling, lower the temperature through well heater more afterwards, thus the temperature met needed for isobutylene etherification with methanol reaction, improve the reaction efficiency of etherification reaction.
Preferably, treat on the connection line between dehydrogenation material inlet and hydrogenation material outlet in MT reconnaissance BE system, be provided with outer row's material mouth, outer row's material mouth is connected with external heavy carbon four tank 50.When fluctuation appears in hydrogenation unit, can, by opening outer row's material mouth, make it be connected with heavy carbon four tank 50, to prevent 1,3 divinyl or other unsaturated hydrocarbons pollute down-stream system, reduce the quantity discharged of follow-up system, are beneficial to cleaning and the maintenance of follow-up system.
In a kind of preferred embodiment of the present invention, as shown in Figure 1, above-mentioned hydrogenation reaction assembly comprises the first hydrogenation reaction tank 61, second hydrogenation reaction tank 62 and First Heat Exchanger 63.Wherein, the first hydrogenation reaction tank 61 is provided with coal-based carbon four feeding mouth and hydrogen feeding mouth.Second hydrogenation reaction tank 62 is positioned at the downstream of the first hydrogenation reaction tank 61, and the second hydrogenation reaction tank 62 is provided with hydrogenation material outlet; First Heat Exchanger 63 is connected between the first hydrogenation reaction tank 61 and the second hydrogenation reaction tank 62.This two-part hydrogenating component, be conducive to making 1 in coal-based carbon four, fully there is hydrogenation reaction in 3 divinyl and other unsaturated hydrocarbons, be converted into alkyl completely, First Heat Exchanger 63 in two hydrogenation reaction tanks is then to ensure that alkene and hydrogen obtain suitable temperature of reaction before entering the second hydrogenation reaction tank 62, improves the efficiency of hydrogenation reaction.
In a kind of preferred embodiment of the present invention, as shown in Figure 1, the dehydrogenation tower assembly in MT reconnaissance BE system comprises dehydrogenation tower body 71, first circulation tank 72 and the second interchanger 73.Wherein, dehydrogenation tower body 71 is provided with treats dehydrogenation material inlet and heavier feeds outlet, and gas light material exports and light recycle material inlet.First circulation tank 72 is provided with gas light material entrance, light recycle material outlet and fuel gas outlet; Gas light material entrance is connected with gas lightweight thing discharge port, and light recycle material outlet is connected with light recycle material inlet.Second interchanger 73 be arranged on gas light material entrance and gas light material export between stream on.
Adopt above-mentioned dehydrogenation tower assembly structure, coal-based carbon four enters in the dehydrogenation tower of dehydrogenation tower assembly and carries out Dehydroepiandrosterone derivative after hydrogenation reaction, avoids being mixed with a small amount of hydrogen in coal-based carbon four and enters downstream participation etherification reaction, reduce the generation of byproduct of reaction.Fuel gas ensure that temperature required in dehydrogenation tower at the first circulation tank 72, second interchanger 73 with circulating in dehydrogenation tower simultaneously, and being exported by the fuel gas on the first circulation tank 72 of timing regularly discharges unnecessary fuel gas, is beneficial to the carrying out of dehydrogenating technology.And the coal-based carbon four fundamental rules after dehydrogenation are got rid of by the heavier feeds outlet on dehydrogenation tower, enter next process procedure.
In a kind of preferred embodiment of the present invention, in MT reconnaissance BE system, also comprise removal of impurities separation system.As shown in Figure 1, this removal of impurities separation system is connected with the MTBE reactant discharge port of MTBE retort 40, comprises the MTBE separation assembly, separating methanol assembly and the C that sequentially arrange
4separation assembly.Enter MTBE separation assembly after iso-butylene and methyl alcohol generation etherification reaction generate MTBE product in coal-based carbon four, reclaim MTBE product, unreacted coal-based carbon 4 mixture and methyl alcohol then enter separating methanol assembly and C subsequently successively
4separation assembly, reclaims the butene-1 in methyl alcohol and coal-based carbon four, butane and heavy C
4.
Preferably, as shown in Figure 1, MT reconnaissance BE separation assembly comprises: tower 82 on tower 81 and catalytic distillation under catalytic distillation.Under catalytic distillation tower 81 sidewall on be provided with first and treat catalytic distillation thing entrance and circulation catalysis material inlet, under catalytic distillation, the top of tower 81 is provided with the first gaseous mixture outlet, and the tower bottom of catalytic distillation is provided with MTBE outlet; On catalytic distillation tower 82 sidewall on be provided with second and treat catalytic distillation thing entrance, on catalytic distillation, tower 82 top is provided with the second gaseous mixture outlet, and catalytic distillation is provided with circulation catalysis material outlet bottom tower 82.Second treats that catalytic distillation thing entrance exports with the first gaseous mixture is connected, and circulation catalysis material outlet is connected with circulation catalysis material inlet, and the second gaseous mixture outlet is connected with follow-up separating methanol assembly.
In actually operating, the MTBE product that generates is reacted and unreacted reactant is introduced into tower 81 catalytic distillation from MTBE retort 40, unreacted methyl alcohol and coal-based carbon 4 mixture are got rid of from the first gaseous mixture outlet at tower catalytic distillation 81 top, the MTBE outlet that MTBE product is then arranged bottom tower catalytic distillation 81 drains in MTBE product-collecting tank, and a kind of preferred scheme first passes through one interchanger at MTBE product after tower catalytic distillation 81 is got rid of, heat exchange is carried out with the mixed gas of the eliminating from MTBE retort 40, not only reduce the temperature of MTBE product, ensure that mixed gas isolates the temperature needed for MTBE product simultaneously.Meanwhile, after this road interchanger, pass through one interchanger at MTBE product again, reduce the temperature of MTBE product further, be beneficial to the recovery of MTBE product.
Further, the coal-based carbon 4 mixture that the first gaseous mixture outlet at tower 81 top is got rid of from catalytic distillation enters tower 82 on catalytic distillation again, on catalytic distillation in tower 82, unreacted iso-butylene and methyl alcohol again react and generate MTBE product, MTBE product to drain under catalytic distillation in tower 81 by being provided with circulation catalysis material outlet bottom tower on catalytic distillation 82, and then entering in MTBE product-collecting tank, coal-based carbon 4 mixture and methyl alcohol are then provided with the second gaseous mixture outlet by tower on catalytic distillation 82 top and enter separating methanol assembly.
Through above-mentioned two-step pretreatment, reclaimed MTBE product to greatest extent, while guarantee MTBE quality product, also improve product production, economic benefit is more remarkable.
MT reconnaissance BE separation assembly also comprises the second circulation tank and the 3rd interchanger.Second circulation tank is provided with gaseous mixture entrance and the outlet of the 3rd gaseous mixture, and the 3rd gaseous mixture outlet is connected with the circulation gas entrance be arranged on catalytic distillation on tower 82 and follow-up separating methanol assembly respectively.3rd interchanger is arranged between the second gaseous mixture outlet and gas mixture entrance.
In MT reconnaissance BE separation assembly, the circulation stream that on 3rd interchanger, the second circulation tank and catalytic distillation, tower 82 three is formed, this circulation loop makes the gas flow on catalytic distillation in tower 82 be a dynamic balance state, to be conducive on catalytic distillation fully carrying out of etherification reaction in tower 82, the 3rd interchanger can also ensure the temperature on catalytic distillation in tower 82 needed for etherification reaction simultaneously.In actually operating, this circulation gas entrance can be arranged on second and treat between catalytic distillation thing entrance and the outlet of the second Gaseous materials,
Preferably, as shown in Figure 1, in MT reconnaissance BE system, separating methanol assembly comprises: dissolve with methanol tank 91 and methanol extraction tank 92.The sidewall of dissolve with methanol tank 91 is provided with methyl alcohol/C
4entrance and recirculated water entrance, top is provided with C
4outlet, bottom is provided with methanol-water outlet, and recirculated water entrance is positioned at methyl alcohol/C
4entrance and C
4between outlet.The sidewall of methanol extraction tank 92 is provided with methanol-water entrance and self-circulating water entrance, top is provided with methanol charge outlet, and bottom is provided with circulating water outlet and self-circulating water outlet, is provided with the 4th interchanger 93 between self-circulating water outlet and self-circulating water entrance; Methanol-water outlet is connected with methanol-water entrance, and circulating water outlet is connected with recirculated water entrance, C
4outlet and follow-up and C
4separation assembly is connected, and methanol charge outlet is connected with Methanol Recovery tank.
Above-mentioned separating methanol assembly can make to be blended in coal-based carbon 4 mixture methyl alcohol by arranging dissolve with methanol tank 91 and methanol extraction tank 92 is separated with coal-based carbon 4 mixture by the mode of dissolving-extracting, and reclaims, reduce material loss to methyl alcohol.
In actually operating, first coal-based carbon 4 mixture after MTBE discrete group and methyl alcohol enter the dissolve with methanol tank 91 in separating methanol assembly subsequently, in order to be beneficial to the abundant dissolving of methyl alcohol, before entering dissolve with methanol tank 91, an interchanger can be set, mixed gas is lowered the temperature.In dissolve with methanol tank 91, methyl alcohol is fully dissolved in water, and coal-based carbon 4 mixture is then by the C of top setting in dissolve with methanol tank 91
4outlet enters to C
4separation assembly; Further, the methanol-water outlet that methanol-water is arranged bottom dissolve with methanol tank 91 enters methanol extraction tank 92, in methanol extraction tank 92, methanol-water enters the 5th interchanger 94 by self-circulating water outlet, methanol-water is heated, realize being separated of methyl alcohol and water, methyl alcohol is exported by methanol charge and enters in methyl alcohol holding tank afterwards, and simultaneously separated recirculated water is then discharged by circulating water outlet and again entered dissolve with methanol tank 91 and carry out recycle.
In the preferred embodiment of the present invention, as shown in Figure 1, the 5th interchanger 94 and an acid-scrubbing cleaning tank is once provided with between circulating water outlet and recirculated water entrance, wherein the 5th interchanger 94 exports with methanol-water and methanol-water entrance communicates simultaneously, recirculated water, when the 5th interchanger 94, carries out heat exchange cooling with the methanol-water from dissolve with methanol tank 91.In the preferred embodiment of one of the present invention, recirculated water is after the 5th interchanger 94 heat exchange, and another road interchanger is lowered the temperature further.Simultaneously because recirculated water dissolves methyl alcohol, recirculated water can be made to show weakly alkaline, so recirculated water enters acid-scrubbing cleaning tank again after twice interchanger, make recirculated water keep neutral always, not only can recycle dissolved water but also can dissolve in dissolve with methanol tank 91 to greatest extent, reclaim methyl alcohol by above step.
Preferably, as shown in Figure 1, the C in MT reconnaissance BE system
4separation system comprises: debutanizing tower 101 and butene-1 rectifying tower 102.Debutanizing tower 101 upper side wall is provided with C
4entrance, bottom is provided with debutylize outlet, top is provided with the first heavy C
4outlet; Butene-1 rectifying tower 102 upper side wall arranges and needs rectifying entrance, top and be provided with that butylene-1 exports, bottom is provided with the second heavy C4 outlet; C4 entrance is connected with the described separating methanol assembly of upstream, and debutylize exports and treats that rectifying entrance is connected.
In actually operating, debutanizing tower 101 is entered after the coal-based carbon 4 mixture got rid of from dissolve with methanol tank 91 and the coal-based carbon four reactant heat exchange from dehydrogenation tower assembly heat up, remove the butane in coal-based carbon 4 mixture, a wherein part for the coal-based carbon 4 mixture after debutylize is by the first heavy C
4outlet enters heavy C
4holding tank, another part then enters butene-1 rectifying tower by debutylize outlet, reclaims butylene-1 wherein in the rectifying tower of butylene-1, and butylene-1 is by the second heavy C
4outlet enters in butene-1 holding tank, and the heavy C of remnants
4then by the second heavy C
4enter heavy C
4in holding tank, reclaim.
Beneficial effect of the present invention is further illustrated below with reference to specific embodiment.
Embodiment 1
Carry out the coal-based C of carbon four supply department
4enter hydrogenation reaction assembly, the hydrogen appropriate with proportioning carries out hydrogenation reaction, after hydrogenation is qualified, material is switched to dehydrogenation tower, the light constituent in the hydrogen of hydrogenation remnants and raw material is removed in dehydrogenation tower, bottom discharge is entered methyltertiarvbutyl ether reactor and carries out etherification reaction, C after etherificate with the methyl alcohol from methyl alcohol supply department after being lowered the temperature by interchanger
4enter tower under catalytic distillation, MTBE product separation is carried out in tower under catalytic distillation, the lower tower bottom extraction of MTBE product autocatalysis distillation enters MTBE products pot, top material enters tower on catalytic distillation, catalytic distillation carries out methyltertiarvbutyl ether reactor in tower further, bottoms material is circulated to lower tower, top methyl alcohol/C
4material enters methanol recovery system, and methyl alcohol returns methyl alcohol supply department and recycles after extraction and recovery, C
4material then enters butene-1 unit, debutanizing tower T, butene-1 rectifying tower, and butene-1 product enters butene-1 products pot from tower top side take-off, heavy C
4the heavy C of extraction at the bottom of tower
4tank.
Comparative example 1
From the coal-based C of carbon four supply department
4enter methyltertiarvbutyl ether reactor and carry out methyltertiarvbutyl ether reactor together with the methyl alcohol from methyl alcohol supply department, C after etherificate
4enter tower under catalytic distillation, MTBE product separation is carried out in tower under catalytic distillation, the lower tower bottom extraction of MTBE product autocatalysis distillation enters MTBE products pot, top material enters tower on catalytic distillation, catalytic distillation carries out methyltertiarvbutyl ether reactor in tower further, bottoms material is circulated to lower tower, top methyl alcohol/C
4material enters methanol recovery system, and methyl alcohol returns methyl alcohol supply department and recycles after extraction and recovery, C
4material then enters hydrogenation reaction assembly, carries out hydrogenation reaction with hydrogen, enters dehydrogenation tower subsequently, removes the light constituent in the hydrogen of hydrogenation remnants and raw material, C afterwards in dehydrogenation tower
4material then enters butene-1 unit, debutanizing tower T, butene-1 rectifying tower, and butene-1 product enters butene-1 products pot from tower top side take-off, heavy C
4the heavy C of extraction at the bottom of tower
4tank.
Under the operating procedure that embodiment 1 is different with comparative example 1, also it detects within every 9 hours, to get first product sample, and get 7 samples under each technique altogether, determine the percentage composition of its different components, end product quality per-cent correlation data is as follows:
In embodiment 1 after first hydrogenation etherificate operating procedure under, the percentage composition of different components in gas product:
In comparative example 1 under the operating procedure of first etherificate back end hydrogenation, the percentage composition of different components in gas product:
| Sampling time | Methyl alcohol % | MTBE | MSBE | Trimethyl carbinol % | C 4％ | DIB％ | Trimerization | C 5+％ |
| ％ | ％ | Thing % | ||||||
| 1 | 0.06 | 84.53 | 0.98 | 3.1 | 0.35 | 4.9 | 1.5 | 4.58 |
| 2 | 0.05 | 85.69 | 1.12 | 1.6 | 0.48 | 4.37 | 2.08 | 4.61 |
| 3 | 0.07 | 86.09 | 1.44 | 1.04 | 0.65 | 3.37 | 2.57 | 4.77 |
| 4 | 0.05 | 86.49 | 1.22 | 0.98 | 0.58 | 3.39 | 2.62 | 4.67 |
| 5 | 0.06 | 87.1 | 1.35 | 0.78 | 0.37 | 3.51 | 3.07 | 3.76 |
| 6 | 0.06 | 86.33 | 1.96 | 0.73 | 0.34 | 3.27 | 3.77 | 3.54 |
| 7 | 0.06 | 86.61 | 1.88 | 0.81 | 0.34 | 3.13 | 3.49 | 3.68 |
Can be found by product quality analysis contrast, the MTBE quality product produced by etherificate production technique after first hydrogenation after transformation is significantly improved, MTBE content: be increased to 92.5% ~ 94.4% by 84% ~ 87%; Effective constituent (the MTBE+MSBE+ trimethyl carbinol) content has brought up to 95.01% ~ 96.63% by 88.41% ~ 89.23% before transforming, and DIB and trimeric total content have been reduced to 1.41% ~ 1.71% by original 6.01% ~ 7.04%, reduce 5 ~ 6% percentage points, quality product reaches the index of the MTBE of cracking c_4 and FCC carbon four production, also the requirement of market as gasoline dope is met, qualified product.Butene-1 quality product is normal, uninfluenced.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a MTBE production system, is characterized in that, described MTBE production system comprises:
Methyl alcohol supply department (10);
Coal-based carbon four supply department (20);
Hydrogen supplying portion (30);
MTBE retort (40), which is provided with methyl alcohol feeding mouth, iso-butylene feeding mouth and MTBE reactant discharge port, described methyl alcohol feeding mouth is connected with described methyl alcohol supply department;
Hydrogenation reaction assembly, which is provided with coal-based carbon four feeding mouth and hydrogen feeding mouth, and hydrogenation material outlet, described coal-based carbon four feeding mouth is connected with described coal-based carbon four supply department (20), and hydrogen feeding mouth is connected with described hydrogen supplying portion (30);
Dehydrogenation tower assembly, which is provided with and treat dehydrogenation material inlet and heavier feeds outlet, described in treat that dehydrogenation material inlet is connected with described hydrogenation material outlet, described heavier feeds exports and is connected with described iso-butylene feeding mouth.
2. system according to claim 1, is characterized in that, described in treat that the connection line between dehydrogenation material inlet and described hydrogenation material outlet is provided with outer row's material mouth, described outer row's material mouth is connected with external heavy carbon four tank (50).
3. system according to claim 1 and 2, is characterized in that, described hydrogenation reaction assembly comprises:
First hydrogenation reaction tank (61), described coal-based carbon four feeding mouth and described hydrogen feeding mouth are positioned on described first hydrogenation reaction tank (61);
Second hydrogenation reaction tank (62), is positioned at the downstream of described first hydrogenation reaction tank (61), and described hydrogenation material outlet is positioned on described second hydrogenation reaction tank (62);
First Heat Exchanger (63), is connected between described first hydrogenation reaction tank (61) and described second hydrogenation reaction tank (62).
4. system according to claim 1 and 2, is characterized in that, described dehydrogenation tower assembly comprises:
Dehydrogenation tower body (71), treat dehydrogenation material inlet and the outlet of described heavier feeds, and gas light material exports and light recycle material inlet described in which is provided with;
First circulation tank (72), which is provided with gas light material entrance, light recycle material outlet and fuel gas outlet; Described gas light material entrance is connected with described gas lightweight thing discharge port, and described light recycle material outlet is connected with described light recycle material inlet;
Second interchanger (73), be arranged on described gas light material entrance and described gas light material export between stream on.
5. system according to claim 2, it is characterized in that, described MTBE reactive system also comprises removal of impurities separation system, described removal of impurities separation system is connected with the MTBE reactant discharge port of described MTBE retort (40), comprises the MTBE separation assembly, separating methanol assembly and the C that sequentially arrange
4separation assembly.
6. system according to claim 5, is characterized in that, described MTBE separation assembly comprises:
Tower (81) under catalytic distillation, under described catalytic distillation tower (81) sidewall on be provided with first and treat catalytic distillation thing entrance and circulation catalysis material inlet, under described catalytic distillation, the top of tower (81) is provided with the first gaseous mixture outlet, and under described catalytic distillation, tower (81) bottom is provided with MTBE outlet;
Tower (82) on catalytic distillation, on described catalytic distillation tower (82) sidewall on be provided with second and treat catalytic distillation thing entrance, on described catalytic distillation, tower (82) top is provided with the second gaseous mixture outlet, and on described catalytic distillation, tower (82) bottom is provided with circulation catalysis material outlet;
Described second treats that catalytic distillation thing entrance exports with described first gaseous mixture is connected, and described circulation catalysis material outlet is connected with described circulation catalysis material inlet, and described second gaseous mixture outlet is connected with follow-up separating methanol assembly.
7. system according to claim 6, is characterized in that, described MTBE separation assembly also comprises:
Second circulation tank, which is provided with gaseous mixture entrance and the outlet of the 3rd gaseous mixture, and described 3rd gaseous mixture outlet is connected with the circulation gas entrance be arranged on described catalytic distillation on tower (82) and follow-up separating methanol assembly respectively;
3rd interchanger, is arranged between described second gaseous mixture outlet and described gas mixture entrance.
8. system according to claim 5, is characterized in that, described separating methanol assembly comprises:
Dissolve with methanol tank (91), the sidewall of described dissolve with methanol tank (91) is provided with methyl alcohol/C
4entrance and recirculated water entrance, top is provided with C
4outlet, bottom is provided with methanol-water outlet, and described recirculated water entrance is positioned at described methyl alcohol/C
4entrance and described C
4between outlet;
Methanol extraction tank (92), the sidewall of described methanol extraction tank (92) is provided with methanol-water entrance and self-circulating water entrance, top is provided with methanol charge outlet, bottom is provided with circulating water outlet and self-circulating water outlet, is provided with the 4th interchanger (93) between described self-circulating water outlet and described self-circulating water entrance;
Described methanol-water outlet is connected with described methanol-water entrance, and described circulating water outlet is connected with described recirculated water entrance, described C
4the C in outlet and downstream
4separation assembly is connected, and described methanol charge outlet is connected with Methanol Recovery tank.
9. system according to claim 8, is characterized in that, described separating methanol assembly comprises:
5th interchanger (94), is arranged between the outlet of described methanol-water and described methanol-water entrance, and communicates with described circulating water outlet and described recirculated water entrance.
10. system according to claim 5, is characterized in that, described C
4separation system comprises:
Debutanizing tower (101), its upper side wall is provided with C
4entrance, bottom is provided with debutylize outlet, top is provided with the first heavy C
4outlet;
Butene-1 rectifying tower (102), its upper side wall arranges and needs that rectifying entrance, top are provided with butene-1 outlet, bottom is provided with the second heavy C
4outlet;
Described C
4entrance is connected with the described separating methanol assembly of upstream, with described, described debutylize outlet treats that rectifying entrance is connected.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510129091.3A CN104803832B (en) | 2015-03-23 | 2015-03-23 | MTBE (methyl tert-butyl ether) production system |
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| CN201510129091.3A CN104803832B (en) | 2015-03-23 | 2015-03-23 | MTBE (methyl tert-butyl ether) production system |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201037131Y (en) * | 2007-04-11 | 2008-03-19 | 河北凯瑞化工有限责任公司 | Modified device for producing methyl t-butyl ether |
| CN102675057A (en) * | 2012-02-25 | 2012-09-19 | 中国石油大学(华东) | Catalytic distillation technique for synthesizing methyl tertiary butyl ether |
| CN103641693A (en) * | 2013-12-05 | 2014-03-19 | 河北海特伟业石化有限公司 | Low-energy-consumption MTBE (methyl tert-butyl ether) production method |
-
2015
- 2015-03-23 CN CN201510129091.3A patent/CN104803832B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201037131Y (en) * | 2007-04-11 | 2008-03-19 | 河北凯瑞化工有限责任公司 | Modified device for producing methyl t-butyl ether |
| CN102675057A (en) * | 2012-02-25 | 2012-09-19 | 中国石油大学(华东) | Catalytic distillation technique for synthesizing methyl tertiary butyl ether |
| CN103641693A (en) * | 2013-12-05 | 2014-03-19 | 河北海特伟业石化有限公司 | Low-energy-consumption MTBE (methyl tert-butyl ether) production method |
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