CN103193581A - Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 - Google Patents
Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 Download PDFInfo
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Abstract
The invention discloses a method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4. The method sequentially comprises the following three working sections: coal-based mixing C4 pretreatment and etherification working section, butene oxidative dehydrogenation working section and butadiene refining working section, wherein the coal-based mixing C4 pretreatment working section sequentially comprises the following steps: (1) removing a C5 component; (2) implementing hydroisomerization; and (3) condensing isobutene; and in the etherification step, isobutene obtained from the top of an isobutene condensation tower is pumped into an etherification tower together with ethanol for an etherification reaction. Furthermore, the invention discloses a combination device for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4. The method can be used for realizing the effective and comprehensive utilization of 1-butene, isobutene, 2-butene and 1,3-butadiene in the coal-based mixing C4 as well as few C5 component, so that the comprehensive utilization rate is improved, and the method is a new trend of comprehensive utilization of the coal-based mixing C4.
Description
Technical field
The invention belongs to chemical production technical field, being specifically related to a kind of is the apparatus and method of raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product.
Background technology
In recent years, along with the lifting of crude oil in China working depth and the progressively raising of ethylene production capacity, by-product carbon four will be more and more abundanter.At present China's carbon four has only about 16% in the utilization ratio aspect the chemical industry, mainly be that iso-butylene is converted into methyl tertiary butyl ether (MTBE), also has the part 1-butylene for the preparation of methylethylketone, the carbon four of most of oil refining process is used as fuel and liquefied gas, and the utilization ratio of industrially developed country such as the U.S., Japan and West Europe has reached 60%.In addition, along with the fast development of China's tire industry, the consumption fast rise of isoprene-isobutylene rubber the demand of high purity butylene alkene monomer is increased year by year, but the high purity butylene alkene monomer mainly relies on import.
Except butadiene extraction, MTBE production technology, China still lacks complexes and the mature technology that maximization carbon four utilizes, and demands developing carbon four downstream fine refinement deep process technologies urgently.How fully, reasonably utilize carbon four resources, excavate the potential value of carbon four-product, improve the oil refining enterprise economic benefit, become one of focus that petrochemical enterprise in China pays close attention to and research of technique direction.Mixed c 4 adopts different comprehensive utilization process routes according to source and each component concentration difference.
Refinery's C-4-fraction is rich in alkane, mainly is Trimethylmethane, and its content generally can both reach 30%～40%.The carbon four of refinery's by-product is produced the stop bracket gasoline additive by etherificate, alkylation except small portion at present, and all the other are directly sold as the oil liquefied gas product mostly, and utilization ratio is lower.The application of refinery C four is except synthesizing iso-butylene the MTBE, and other utilizations are more difficult, mainly is alkane especially Trimethylmethane to be converted into alkene or normal butane through dehydrogenation, is converted into Trimethylmethane by isomery.
Steam cracking is made the carbon four of the device by-product of ethene, and contained alkene and divinyl total amount be up to 95%, and only contains 3% the alkane of having an appointment.Therefore, the alkene utilization in the cracking c_4 utilizes much easier than refinery C four, and utilization ratio is also high.At first carry out the extracting of divinyl in the world for cracking c_4, the gained divinyl mainly as the raw material of synthetic rubber or resin, is converted into iso-butylene MTBE or polymer gasoline then, and last a small amount of alkane is incorporated in the refinery C four.The existing technology of China mainly is that carbon four raffinates are used for the synthetic of MTBE, consume iso-butylene wherein, residue carbon four adopts the separable 1-butylene that goes out polymerization-grade of precise distillations or extracting rectifying, contains a large amount of 2-butylene in the last carbon four and a small amount of normal butane mainly directly uses as liquefied gas.In recent years abroad at butene dimerization hydrogenation preparing alkylate oil technology, carbon four and carbon five, carbon four such as preparing low-carbon olefin by catalytically cracking technology, ethene and preparing propylene by butene disproportionation utilize the research and development of new way to obtain impressive progress, part industrialization or industrialization soon.
Coal-based mixed c 4 is important carbon four sources except refinery C four and cracking of ethylene carbon four, and the few oil of the rich coal of China is according to estimating that the Coal Chemical Industry development has good prospect over the next several years.
The mixed c 4 about by-product 5.5% (to methyl alcohol) simultaneously in methanol-to-olefins (MTO) process, different with naphtha cracking ethene processed is, and this mixed c 4 does not contain divinyl and iso-butylene content is also extremely low, and main ingredient butene-1, butene-2 account for 90%.Be translated into the economy that ethene, propylene or other high value added product can further improve coal alkene project processed again by the course of processing.The technology that can adopt has at present: with DMTO-II generation technique, olefin metathesis technology (OCT), olefin cracking technology (OCP) and the production 2-propyl enanthol (2-PH) etc. of carbon four, C5 fraction freshening.Each component concentration contrast in coal-based mixed c 4, refinery C four and the cracking of ethylene carbon four, wherein coal-based carbon four contains suitable-2-butylene 28.25%, and anti--2-butylene 36% sees the following form 1:
Table 1
| ? | Coal-based carbon four (%) | Refinery C four (%) | Cracking c_4 (%) |
| Normal butane | 5.5 | 10 | 2 |
| Trimethylmethane | 0 | 34 | 1 |
| 1-butylene | 22.5 | 13 | 14 |
| Iso-butylene | 6.25 | 15 | 22 |
| 2-butylene | 64.25 | 28 | 11 |
| 1,3-butadiene | 1.5 | 0 | 50 |
Disproportionation reaction is under catalyst action alkene mixture to be converted into new alkene mixture, and for example ethene, 2-butylene generation disproportionation reaction are produced bimolecular propylene.The OCT that Lummus develops (Olefins Conversion Technology) is the representative of olefin metathesis technology, and it is WO3 and the MgO that is stated from the diatomite that this technology adopts fixed-bed reactor, catalyzer.Conversion of ethylene is that the selectivity of propylene selectivity nearly 100%, that butylene is converted into propylene is nearly 97% in the OCT technology, butylene total conversion rate 85%-92%.
The olefin cracking technology (OCP, Olefin Cracking Process) that UOP and TOTAL develop jointly has been built industrial demonstration unit at Belgian Antwerp.This technology adopts special-purpose ZSM-5 molecular sieve catalyst, under 500 ℃～600 ℃, 0.1～0.5MPa reaction conditions, the C4-C8 raw material contact generation scission reaction with catalyzer in fixed-bed reactor, be converted into the light olefin based on propylene.When technology combines, the total recovery of ethene and propylene being brought up to more than 90% by 80% this Technology and methanol-to-olefins (MTO), propene yield brings up to 60% by 3O%～50%.
With the butylene be raw material to adopt carbonylic preparation method to produce the 2-propyl enanthol be both economical method, its synthetic method is similar with the method that with the propylene is raw material production fourth octanol: C 4 olefin with CO carbonylation takes place under the effect of catalyzer or hydroformylation reaction generates the valeral mixture.Valeraldehyde or isovaleric aldehyde generate Pentyl alcohol or primary isoamyl alcohol with hydrogen reaction under carrying metal (Pd, Ni) catalyst action; Valeraldehyde obtains capraldehyde, capraldehyde through condensation and obtains mixing decyl alcohol based on the 2-propyl enanthol through hydrogenation, rectifying.
The present invention improves the utilization ratio of mixed c 4 according to the component concentration of coal-based mixed c 4, and designs the operational path that a kind of new coal-based mixed c 4 fully utilizes.
Summary of the invention
The object of the present invention is to provide a kind of is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the apparatus and method of 3-divinyl and Ethyl Tertisry Butyl Ether, this method is with the 1-butylene in the coal-based mixed c 4, iso-butylene, 2-butylene, 1,3-divinyl and small amount of carbon were all carried out effective comprehensive utilization in fifty percent minute, having improved its comprehensive utilization ratio, is the new direction of coal-based mixed c 4 comprehensive utilization.
The present invention is achieved by the following technical solutions:
Provided by the invention a kind of be raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the method of 3-divinyl and Ethyl Tertisry Butyl Ether, comprise following three workshop sections successively: coal-based mixed c 4 pre-treatment and etherificate workshop section, butylene oxidation-dehydrogenation workshop section, the refining workshop section of divinyl, described coal-based mixed c 4 pre-treatment and etherificate workshop section comprise coal-based mixed c 4 pre-treatment step and etherification step;
Described coal-based mixed c 4 pre-treatment step comprises successively:
(1) removal of carbon five components pump into decarburization five towers with the carbon four in the coal-based mixed c 4 storage tank, and this tower working pressure is 3-6atm, and tower top temperature keeps 40-45 ℃, and column bottom temperature is 75-90 ℃;
(2) hydro-refining isomery reaction enters the hydro-refining isomery reaction device from the discharging of step (1) decarburization five column overhead, and 1-butylene is transformed to 2-butylene, add catalyzer, described catalyzer is the Pd/Al2O3 of SiO2 load, temperature of reaction is 80-100 ℃, and pressure-controlling is at 1-2MPa;
(3) iso-butylene concentrate enters the iso-butylene concentration tower, the working pressure 3-6atm of concentration tower from the discharging of step (2) hydro-refining isomery reaction device, tower top temperature 30-40 ℃, temperature at the bottom of the tower is 40-60 ℃, obtains concentration 20%-50% iso-butylene from iso-butylene concentration tower cat head, obtains 2-butylene at the bottom of the tower;
Described etherification step, the iso-butylene from described step (3) iso-butylene concentration tower cat head obtains rises to 45 ℃ by interchanger with temperature, together pump into the etherificate tower with ethanol, add catalyzer to described etherificate tower, described catalyzer is strongly acidic cation-exchange A15, and reaction generates ETBE.
According to provided by the invention be raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the method of 3-divinyl and Ethyl Tertisry Butyl Ether, described butylene oxidation-dehydrogenation workshop section for the 2-butylene that at the bottom of described step (3) tower, obtains through behind the oxidative dehydrogenation, washing, compression, oil wash and desorb obtain the crude product 1,3-butadiene.
According to provided by the invention be raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the method of 3-divinyl and Ethyl Tertisry Butyl Ether, the crude product 1 of the refining workshop section of described divinyl for described butylene oxidation-dehydrogenation workshop section is obtained, the 3-divinyl is successively through first extraction tower, first stripping tower is removed crude product 1, carbon three hydrocarbon and butane in the 3-divinyl, then through second extraction tower, second stripping tower is removed in the crude product easily molten hydrocarbons, preferably remove suitable-2-butylene and obtain the product 1,3-butadiene through taking off heavies column.
According to provided by the invention be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, the cat head discharging of described etherificate tower utilizes membrane separation apparatus to carry out membrane sepn, reclaims ethanol and hydrocarbons; Separate the ethanol that obtains and mix with fresh ethanol, the recycling membrane sepn joins the etherificate tower after removing water from top.
According to provided by the invention be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, the cat head discharging of described etherificate tower utilizes membrane sepn, obtains hydrocarbons and delivers to described butylene oxidation-dehydrogenation workshop section.
According to provided by the invention be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, described etherificate tower is catalytic rectifying tower.
According to provided by the invention be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, the C5 that obtains from decarburization five tower reactors in the described step (1) and above component are sent into the liquid waste disposal pond.
According to provided by the invention be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, the hydro-refining isomery reaction device is selected the tubulation fixed-bed reactor for use in the described step (2).
According to provided by the invention be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, described ethanol is selected from dehydrated alcohol or 95% ethanol.
It is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product that the present invention also provides a kind of, the associated plant of 3-divinyl and Ethyl Tertisry Butyl Ether, described associated plant is formed by connecting by coal-based mixed c 4 pre-treatment and etherificate workshop section device, butylene oxidation-dehydrogenation workshop section device, the refining workshop section of divinyl device successively, described coal-based mixed c 4 pre-treatment and etherificate workshop section device comprise and are provided with carbon four opening for feeds, are used for decarburization five towers of removal of carbon five components; The hydro-refining isomery reaction device that is used for 1-butylene is converted into 2-butylene in described decarburization five column overhead by pipe connection; Described hydro-refining isomery reaction device connects the iso-butylene concentration tower, and described concentration tower cat head connects and is used for the etherificate tower that iso-butylene and ethanol carry out etherification reaction, connects at the bottom of the tower and is used for the butylene oxidation-dehydrogenation workshop section device that 2-butylene carries out oxidizing reaction; Described etherificate cat head end is connected with the membrane separation apparatus that reclaims ethanol and hydrocarbons, and the bottom arranges the etherification product discharge port.
According to provided by the invention be the associated plant of raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, preferably, described hydro-refining isomery reaction device is calandria type fixed bed reactor, this reactor adopts annular tubulation to distribute.
Provided by the invention a kind of be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether (ETBE) with the coal-based mixed c 4 of DMTO by-product, comprise three workshop sections: carbon four pre-treatment and etherificate workshop section, butylene oxidation-dehydrogenation workshop section, the refining workshop section of divinyl.Interim reactive distillation and infiltration evaporation membrane coupling technique are used for iso-butylene and ethanol etherificate ETBE processed with reference to infiltration vaporization membrane technology (comprising separating of second alcohol and water, ethanol and hydrocarbons) and pertinent literature.
Provided by the invention a kind of be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether (ETBE) with the coal-based mixed c 4 of DMTO by-product, described carbon four pre-treatment and the concrete technical process of etherificate workshop section are as follows:
(1) decarburization five components: the raw material from the C4 storage tank pumps into decarburization five towers, and this tower working pressure is 4atm, and tower top temperature keeps 41.8 ℃, 84.6 ℃ of tower reactors.Obtain C5 and above component in tower reactor, send into liquid waste disposal.
(2) hydro-refining isomery reaction: the cat head discharging enters the hydro-refining isomery reaction device.Reactor is selected the tubulation fixed bed for use, and catalyzer uses the Pd/Al2O3 of SiO2 load, and temperature of reaction is 90 ℃, and pressure-controlling is at 1.2MPa.1-butylene transforms to 2-butylene in the reactor, and with the hydrogenation side reaction of 1,3-butadiene.
(3) iso-butylene concentrate: material enters the iso-butylene concentration tower subsequently, working pressure 4atm, 34.9 ℃ of tower top temperatures, at the bottom of the tower 45.13 ℃.Through concentration tower, it is 33.6% iso-butylene that cat head obtains concentration, pumps into the etherificate tower.The iso-butylene massfraction is 883PPM only at the bottom of the tower, delivers to liquid waste disposal.
(4) reactive distillation and infiltrating and vaporizing membrane coupling: the etherificate tower is catalytic rectifying tower, and iso-butylene and ethanol synthesis generate ETBE.Catalyzer adopts strongly acidic cation-exchange A15.Tower reactor obtains the ETBE product of massfraction 99.5%.The cat head discharging then utilizes membrane sepn, and ethanol is separated in order to reclaim ethanol with other hydrocarbons.Separate the ethanol that obtains and mix with fresh ethanol, utilize membrane sepn to remove water, form azeotrope to prevent water and ETBE, add the etherificate tower subsequently from top, hydrocarbons then mixes with iso-butylene concentrate tower bottoms delivers to butylene oxidation-dehydrogenation workshop section.
The present invention is different according to coal-based carbon four raw materials and refinery C four and petroleum cracking carbon four-component, butadiene content is few, so raw material need not traditional divinyl extracting link in handling, and coal-based carbon four raw materials are formed based on 1-butylene and cis and trans 2-butylene, account for 95%.So we have adopted the main road line of butylene oxidation-dehydrogenation 1,3-butadiene processed at the characteristics of coal-based carbon four raw materials.In order to improve raw material availability, we consider the iso-butylene etherificate methyl tertiary butyl ether processed (ETBE) that utilizes content 6.22% in the raw material.
According to method provided by the invention, when selecting herein the science and engineering skill and designing, find to have certain technical difficult problem and proposed corresponding solution in the actual application.
The method according to this invention is produced the iso-butylene content of ETBE necessity greater than 10%: the mass fraction of iso-butylene is 6.22% in coal-based carbon four raw materials, is only second to 1-butylene and 2-butylene, then can't improve the comprehensive utilization degree for carbon four raw materials as if not being used.Conversion for isobutene is very high in the etherification reaction, and for the different C-4-fraction of isobutylene concentration, speed of reaction is also different in the etherification procedure, and concentration height then speed of reaction is fast, but little for the influence degree of isobutene conversion.It may be noted that especially, when iso-butylene content is lower than 10%(w), isobutene conversion can sharply descend.Iso-butylene contains quantity not sufficient 10% in coal-based carbon four raw materials, therefore directly etherificate certainly will can not get very high transformation efficiency, and do not allow the existence of iso-butylene in the oxydehydrogenation, according to method provided by the invention with the iso-butylene concentrate, reach required reaction density and used again, realize the comprehensive utilization of isopropylcarbinol.
The hydro-isomerization unit that increases before etherificate in the method provided by the invention under the situation that a small amount of hydrogen exists, is converted into 1-butylene 2-butylene and passes through rectifying separation, and cat head obtains the isobutene reaction gas (20%-50%) of concentrate, and discharging is 2-butylene at the bottom of the tower.According to experiment showed, that this reaction is thermopositive reaction, low temperature is favourable for reaction.Pass through calculation of thermodynamics simultaneously, find 1-butylene to instead-equilibrium conversion of 2-butylene is higher, spontaneous direction is favourable for transforming.In addition, this reaction can also reach and remove that a small amount of 1,3-butadiene and alkynes prevent from etherification reaction is produced dysgenic effect in the unstripped gas except can the concentrate iso-butylene.Simultaneously, because the boiling point of 1-butylene and iso-butylene only differs from 0.6 ℃, relative volatility has only 1.005, adopts traditional rectificating method to be difficult to its separation, if adopt precise distillation can make energy consumption excessive, can well avoid this to separate a difficult problem and by hydro-isomerization 1-butylene is converted into 2-butylene.
According to method provided by the invention, realize the utilization of carbon five in the coal-based mixed c 4 raw material: contain the carbon five above components about 2.26% in the raw material, consider that the added value of carbon five is also very high.It has interference effect for back oxydehydrogenation flow process simultaneously, does not therefore wish that it enters next workshop section.One decarburization, five towers need be set, and it specifically arranges the position multiple choices, can be arranged at before the hydro-refining isomery reaction device, also can be arranged at after the reactor.The concrete position of selecting should determine according to required operational condition and corresponding cost of equipment.The present invention has all carried out corresponding simulation for two kinds of situations, and it is minimum to found that decarburization five towers are arranged at the required rectifying tower number of theoretical plate of optimal operating condition in the reactor, so remove carbon five before being chosen in reaction.
Selection according to etherificate tower reaction feed alcohol concn in the method provided by the invention: the isobutene reaction in the etherificate tower in ethanol and the unstripped gas generates Ethyl Tertisry Butyl Ether (ETBE) and realize rectifying separation in tower.Ethanol can form azeotrope with water or ETBE under the normal pressure, separates to have certain difficulty.Control condition is improper can to make that then the cat head discharging is entirely the azeotrope of ethanol and ETBE, and waste ETBE also is unfavorable for the recycling of ethanol simultaneously.The selection of feed ethanol concentration is very important, select dehydrated alcohol can avoid the influence of water in the component, eliminate the possibility that forms azeotrope with water, yet but improved our production cost greatly, because the price of dehydrated alcohol is very high, generalized case is directly bought about 95% industrial alcohol as raw material, more can save cost, but for operating and designing and brought very big challenge, be difficult to obtain highly purified ETBE, can only obtain corresponding azeotrope, see accompanying drawing.
In order to utilize cheap 95% to carry out normal etherification reaction, the mode of our selective reaction rectifying and infiltration evaporation coupling is handled etherificate.By the azeotropic mixture of the continuous separating alcohol of infiltrating and vaporizing membrane and ETBE, and then make reaction and separate and can realize synchronously, this is a kind of energy-conservation and high-efficiency method.
Beneficial effect of the present invention:
Provided by the invention is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the apparatus and method of 3-divinyl and Ethyl Tertisry Butyl Ether, this method is with the 1-butylene in the coal-based mixed c 4, iso-butylene, 2-butylene, 1,3-divinyl and small amount of carbon were all carried out effective comprehensive utilization in fifty percent minute, having improved its comprehensive utilization ratio, is the new direction of coal-based mixed c 4 comprehensive utilization.
Description of drawings
Fig. 1 be provided by the invention a kind of be the integrated artistic schema of raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether method with the coal-based mixed c 4 of DMTO by-product;
Fig. 2 is the coal-based mixed c 4 pre-treatment of method and the technical process schema of etherificate workshop section of the invention provides shown in Figure 1;
Fig. 3 is coal-based mixed c 4 pre-treatment and the etherificate workshop section device schema that the invention provides associated plant.
In the drawings: T1101-decarburization five towers, R1101-hydro-refining isomery reaction device, T1102-iso-butylene concentration tower, T1103-etherificate tower, M1101-first membrane separation apparatus, M1102-second membrane separation apparatus.
Embodiment
With reference to accompanying drawing, provided by the invention a kind of be the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, comprise following three workshop sections successively: 1, coal-based mixed c 4 pre-treatment and etherificate workshop section; 2, butylene oxidation-dehydrogenation workshop section; 3, the refining workshop section of divinyl.
1, coal-based mixed c 4 pre-treatment and etherificate workshop section comprise coal-based mixed c 4 pre-treatment step and etherification step; Coal-based mixed c 4 pre-treatment step comprises successively:
(1) removal of carbon five components pump into decarburization five towers with the carbon four in the coal-based mixed c 4 storage tank, and this tower working pressure is 4atm, and tower top temperature keeps 41.8 ℃, and column bottom temperature is 84.6 ℃;
(2) hydro-refining isomery reaction enters the hydro-refining isomery reaction device from the discharging of step (1) decarburization five column overhead, and 1-butylene is transformed to 2-butylene, add catalyzer, described catalyzer is the Pd/Al2O3 of SiO2 load, temperature of reaction is 90 ℃, and pressure-controlling is at 1.2MPa;
(3) iso-butylene concentrate enters the iso-butylene concentration tower, the working pressure 4atm of concentration tower from the discharging of step (2) hydro-refining isomery reaction device, 34.9 ℃ of tower top temperatures, temperature at the bottom of the tower is 45.13 ℃, obtains concentration 20%-50% iso-butylene from iso-butylene concentration tower cat head, obtains 2-butylene at the bottom of the tower;
Etherification step is the iso-butylene that obtains from step (3) iso-butylene concentration tower cat head, by interchanger temperature is risen to 45 degree, together pump into the etherificate tower with ethanol, add catalyzer to described etherificate tower, described catalyzer is strongly acidic cation-exchange A15, and reaction generates ETBE.
2, butylene oxidation-dehydrogenation workshop section: the 2-butylene that obtains at the bottom of step (3) tower from coal-based mixed c 4 pre-treatment step is through behind the oxidative dehydrogenation, and washing, compression, oil wash and desorb obtain the crude product 1,3-butadiene.
Butylene and oxygen by reactor, carry out oxidative dehydrogenation earlier, generate divinyl under the effect of catalyzer, and after condensed gas-liquid two-phase separated, liquid phase entered water-cooled and washes acid tower and mix with its still liquid, and gas phase enters water-cooled and washes bottom the acid tower.After generating gas fully a large amount of moisture and flush away acid, ketone and part aldehydes being removed in cooling in tower, from the cat head compression section that goes out to make a return journey.Generation gas behind the pressure-raising enters the oil-absorption tower bottom and generates gas after absorbing the oil absorption, is disposed to fiery cabinet.The rich oil that comes out at the bottom of the tower enters desorption tower and carries out desorb.Obtain the crude product divinyl from desorption tower.
3, the refining workshop section of divinyl: the crude product 1 that butylene oxidation-dehydrogenation workshop section is obtained, the 3-divinyl is successively through first extraction tower, first stripping tower is removed crude product 1, carbon three hydrocarbon and butane in the 3-divinyl, then through second extraction tower, second stripping tower is removed in the crude product easily molten hydrocarbons, preferably removes suitable-2-butylene and obtains top grade straight product 1,3-butadiene through taking off heavies column.
Provided by the invention is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the apparatus and method of 3-divinyl and Ethyl Tertisry Butyl Ether, this method is with the 1-butylene in the coal-based mixed c 4, iso-butylene, 2-butylene, 1,3-divinyl and small amount of carbon were all carried out effective comprehensive utilization in fifty percent minute, having improved its comprehensive utilization ratio, is the new direction of coal-based mixed c 4 comprehensive utilization.
Claims (10)
1. one kind is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the method of 3-divinyl and Ethyl Tertisry Butyl Ether, comprise following three workshop sections successively: coal-based mixed c 4 pre-treatment and etherificate workshop section, butylene oxidation-dehydrogenation workshop section, the refining workshop section of divinyl is characterized in that:
Described coal-based mixed c 4 pre-treatment and etherificate workshop section comprise coal-based mixed c 4 pre-treatment step and etherification step;
Its described coal-based mixed c 4 pre-treatment step comprises successively:
(1) removal of carbon five components pump into decarburization five towers with the carbon four in the coal-based mixed c 4 storage tank, and this tower working pressure is 3-6atm, and tower top temperature keeps 40-45 ℃, and column bottom temperature is 75-90 ℃;
(2) hydro-refining isomery reaction enters the hydro-refining isomery reaction device from the discharging of step (1) decarburization five column overhead, and 1-butylene is transformed to 2-butylene, add catalyzer, described catalyzer is the Pd/Al2O3 of SiO2 load, temperature of reaction is 80-100 ℃, and pressure-controlling is at 1-2MPa;
(3) iso-butylene concentrate enters the iso-butylene concentration tower, the working pressure 3-6atm of concentration tower from the discharging of step (2) hydro-refining isomery reaction device, tower top temperature 30-40 ℃, temperature at the bottom of the tower is 40-60 ℃, obtains concentration 20%-50% iso-butylene from iso-butylene concentration tower cat head, obtains 2-butylene at the bottom of the tower;
Its described etherification step, the iso-butylene from described step (3) iso-butylene concentration tower cat head obtains rises to 45 ℃ by interchanger with temperature, together pump into the etherificate tower with ethanol, add catalyzer to described etherificate tower, described catalyzer is strongly acidic cation-exchange A15, and reaction generates ETBE.
2. according to claim 1 is the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, it is characterized in that,
Described butylene oxidation-dehydrogenation workshop section for the 2-butylene that at the bottom of described step (3) tower, obtains through behind the oxidative dehydrogenation, washing, compression, oil wash and desorb obtain the crude product 1,3-butadiene.
The crude product 1 of the refining workshop section of described divinyl for described butylene oxidation-dehydrogenation workshop section is obtained, the 3-divinyl is successively through first extraction tower, first stripping tower is removed crude product 1, carbon three hydrocarbon and butane in the 3-divinyl, then through second extraction tower, second stripping tower is removed in the crude product easily molten hydrocarbons, preferably removes suitable-2-butylene and obtains the product 1,3-butadiene through taking off heavies column.
3. according to claim 1 is the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, it is characterized in that the cat head discharging of described etherificate tower utilizes membrane separation apparatus to carry out membrane sepn, reclaims ethanol and hydrocarbons; Separate the ethanol that obtains and mix with fresh ethanol, the recycling membrane sepn joins the etherificate tower after removing water from top.
4. according to claim 3 is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the method of 3-divinyl and Ethyl Tertisry Butyl Ether, it is characterized in that the cat head discharging of described etherificate tower utilizes membrane sepn, obtain hydrocarbons and deliver to described butylene oxidation-dehydrogenation workshop section.
5. according to claim 1 is the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, it is characterized in that described etherificate tower is catalytic rectifying tower.
6. according to claim 1 is the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, it is characterized in that the C5 that obtains from decarburization five tower reactors in the described step (1) and above component are sent into the liquid waste disposal pond.
7. according to claim 1 is the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, it is characterized in that, the hydro-refining isomery reaction device is selected the tubulation fixed-bed reactor for use in the described step (2).
8. according to claim 1 is the method for raw material coproduction 1,3-butadiene and Ethyl Tertisry Butyl Ether with the coal-based mixed c 4 of DMTO by-product, it is characterized in that described ethanol is selected from dehydrated alcohol or 95% ethanol.
One kind according to claim 1 be raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the associated plant of 3-divinyl and Ethyl Tertisry Butyl Ether, described associated plant is formed by connecting by coal-based mixed c 4 pre-treatment and etherificate workshop section device, butylene oxidation-dehydrogenation workshop section device, the refining workshop section of divinyl device successively, it is characterized in that, described coal-based mixed c 4 pre-treatment and etherificate workshop section device comprise and are provided with carbon four opening for feeds, are used for decarburization five towers of removal of carbon five components; The hydro-refining isomery reaction device that is used for 1-butylene is converted into 2-butylene in described decarburization five column overhead by pipe connection; Described hydro-refining isomery reaction device connects the iso-butylene concentration tower, and described concentration tower cat head connects and is used for the etherificate tower that iso-butylene and ethanol carry out etherification reaction, connects at the bottom of the tower and is used for the butylene oxidation-dehydrogenation workshop section device that 2-butylene carries out oxidizing reaction; Described etherificate cat head end is connected with the membrane separation apparatus that reclaims ethanol and hydrocarbons, and the bottom arranges the etherification product discharge port.
10. according to claim 9 is raw material coproduction 1 with the coal-based mixed c 4 of DMTO by-product, the associated plant of 3-divinyl and Ethyl Tertisry Butyl Ether, it is characterized in that described hydro-refining isomery reaction device is calandria type fixed bed reactor, this reactor adopts annular tubulation to distribute.
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| CN2013101303007A CN103193581A (en) | 2013-04-15 | 2013-04-15 | Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 |
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| CN2013101303007A CN103193581A (en) | 2013-04-15 | 2013-04-15 | Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 |
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| CN114456044A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Ether production process by utilizing membrane separation alcohol/mixed light hydrocarbon |
| CN114456044B (en) * | 2020-10-22 | 2024-04-09 | 中国石油化工股份有限公司 | Ether production process using membrane separation alcohol/mixed light hydrocarbon |
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