CN103214333A - System and process for gas-solid separation and heat exchange of alkene product prepared from organic oxygen-containing compound - Google Patents
System and process for gas-solid separation and heat exchange of alkene product prepared from organic oxygen-containing compound Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a system and process for the gas-solid separation and heat exchange of an alkene product prepared from an organic oxygen-containing compound. The system sequentially comprises at least one whirlwind gas-solid separator, at least one heat exchanger, at least one filter, at least one quench tower and at least one water scrubbing tower, wherein the whirlwind gas-solid separators are used for separating fine catalyst particles and/or fine catalyst powder from a product gas; and the filters are used for further separating the fine catalyst particles and/or the fine catalyst powder from the product gas. The system and process which are disclosed by the invention can prevent the bottoms of the quench towers, the trays of the water scrubbing towers and various heat exchangers from being blocked because a large quantity of fine catalyst particles and/or fine catalyst powder contained in the product gas enter the quench towers and the water scrubbing towers and prevent the abnormal device operation caused due to the blockage, thereby reducing the cost and labor intensity of equipment cleaning operation.
Description
Technical field
The present invention relates to a kind of organic oxygen-containing compound, for example methyl alcohol and/or gas-solid separation of dme system olefin product and heat-exchange system, the invention still further relates to a kind of organic oxygen-containing compound, for example methyl alcohol and/or gas-solid separation of dme system olefin product and heat-exchanging process.
Background technology
Organic oxygen-containing compound, for example methyl alcohol and/or dme system alkene technology have been opened up the new technology route by the basic Organic Chemicals of coal production, and wherein typical technology is methanol-to-olefins (MTO).Usually, the MTO complete set technology is made up of reaction technology and isolation technique.Reaction technology is a core with catalyzer development and reactor development and Design, is the raw material production alkene mixture with methyl alcohol; Product distributes and purity requirement then is the basis of exploitation separating technology.
The MTO reaction at first is to generate dme by methanol dehydration, and the equilibrium mixture of dme and methyl alcohol continues to react then, is converted into the low-carbon (LC) mixed olefins based on ethene and propylene.A spot of low-carbon alkene further generates saturated alkane, aromatic hydrocarbons and high olefin by reactions such as polycondensation, cyclisation, dehydrogenation, alkylation, hydrogen transferences, and a small amount of carbon deposit reaction is also arranged.Dynamics research shows: the MTO on live catalyst is a kind of rapid reaction, and total first order reaction speed of methanol conversion is about 250m
2/ m
3Catalyzer second.
The whole process of MTO technology can be divided into reaction-regeneration system and reaction gas separation system two portions.Reactive moieties has only gas-solid two-phase, and this catalyzed reaction is thermopositive reaction.The catalyzer of inactivation needs combustion charcoal regeneration in fluid bed regenerator, then, returns fluidized-bed reactor and continues reaction.Reactor and revivifier all are provided with heat-transfering device.
It is the technology of low-carbon alkene through methanol conversion that MTO is actually by synthetic gas.Some famous oil and chemical companies in the world, all drop into substantial contribution and personnel as Exxon Mobil Corporation (Exxon – Mobil), BASF AG (BASF), AP Oil company (UOP) and Hydro company (Norsk Hydro), carried out years of researches.
For example, nineteen ninety-five, it is 0.75 ton/day demonstration unit that UOP and Norway Norsk Hydro company cooperate to build up a cover methyl alcohol working ability, this device continuous operation 90 days, and methanol conversion is near 100%, and the carbon back mass yield of ethene and propylene reaches 80%.This process using fluidized-bed reactor and revivifier design, reaction heat is taken out of and is reclaimed by the steam that produces, and the catalyzer of inactivation is sent to coke-burning regeneration in the fluid bed regenerator, returns fluidized-bed reactor then and continues reaction.Whole product gas flow mixture is before separating, need by a special feed stream interchanger, wherein, most of moisture and inert substance, for example remaining catalyst fines are eliminated, then, gaseous product further dewaters through the solution-air knockout tower, and soda-wash tower takes off CO, enters the product recovery zone after the gaseous product drying.This workshop section flow through demethanizing tower, deethanizing column, acetylene saturator, ethylene separation tower, propylene knockout tower, depropanizing tower and debutanizing tower.Oxygenatedchemicals also is removed in compression section.
It is reported that the MTO process products of UOP/Hydro is formed comparatively simple, dopant species and content are less, realize that more easily product separation reclaims, and can adjust C in the reaction product in relative broad range
2Product and C
3The ratio of product; The output ratio of alkene.The SAPO-34 catalyzer of UOP/Hydro company research and development has suitable inner duct scantlings of the structure and solid acid intensity, can reduce the low-carbon alkene oligomerisation, improves the selectivity that generates alkene.Afterwards, UOP/Hydro company has developed new catalyst MTO – 100 again on SAPO – 34 catalyzer bases, and new catalyst MTO – 100 can make the selectivity of ethene and propylene reach 80%.
1998, adopt the 200 kilotons/year full scale plant (by the ethene output) of UOP/Hydro technology to be constructed and put into operation.Europe chemical technology company adopts the MTO technology of UOP/Hydro company to build 7500 tons/day MTO production equipment (by material benzenemethanol) in Nigeria, wherein, methyl alcohol is as the charging of MTO device, the ethene of MTO device and propylene designed productive capacity are 400,000 tons/year, and this device also was constructed and put into operation in 2007.The Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences has finished the MTO pilot scale during " eight or five ", cooperated to have built industrial scale in Shaanxi by the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, the emerging Coal Chemical Industry development in science and technology in Shaanxi limited liability company and Luoyang Petrochemical engineering corporation of SINOPEC and count 15000 tons/year DMTO industrial test device with methanol feedstock in 2005.This device passed through national-level appraisal on August 23rd, 2006 also in l2 month commissioning run test in 2005.This device has been realized nearly 100% methanol conversion on the industrial test device of 50 of day processing methyl alcohol, low-carbon alkene (ethene, propylene, butylene) selectivity reaches more than 90%.It is reported, settled Yulin by honest derived energy chemical group, Shaanxi coal industry chemical industry group, joint 3,000,000 tons of methyl alcohol of year processing and the alkene project of carrying out of Shaanxi Province's investor group.
In general, organic oxygen-containing compound system alkene technology is increasingly mature, but and heavy industrialization or business-like degree have been reached, particularly various MTO technologies, its technology is ripe more, the industrialization experience is abundanter, and at present, the most representative MTO technology mainly comprises: UOP/Hydro technology, change institute's (DMTO) technology and ExxonMobil technology greatly.
At present, though MTO technology is ripe, carry out also having run in heavy industrialization or the business-like process the gas-solid separation problem of practical problems, especially product gas on some engineerings in MTO technology.The MTO reacting middle catalyst is easy to the carbon distribution inactivation, need catalyzer is carried out successive reaction, regenerative operation, in fluidized reaction-regeneration system, the direct impact of granules of catalyst and catalyzer cause catalyzer that the loss of fine powder in use takes place in the wearing and tearing that the equipment surface motion produces.Particle diameter less than 10 microns, particularly less than 5 microns be difficult to they are separated from product gas with conventional gas-solid tripping device, for example cyclonic separator, and these catalyst fines and/or fine powder by the product band of gas to product separating technique middle and lower reaches workshop section, when for example taking in quench tower, water wash column, quenched water wet cyclone and the various interchanger, can cause these plant efficiencies reductions, operational anomaly, or even equipment stops up and the maintenance of must not stopping increase labour intensity, increase cost.Therefore, MTO product gas is held the catalyst fines wrapped up in and/or fine powder under the arm after leaving reactor, preferably as early as possible with the product gas phase separation, arrive product separating technique middle and lower reaches workshop section to avoid them.
Many researchers has been done useful exploration and research on the problems referred to above, for example CN1942558B discloses above-mentioned catalyst fines and reclaims and recycle through wet scrubbing; CN101563306A discloses to hold under the arm and has wrapped the MTO product gas of stating catalyst fines and/or fine powder and contact with the liquid quenching medium of neutralization, thereby above-mentioned catalyst fines and/or fine powder are dammed in the liquid quenching medium stream of neutralization, and then realize itself and the separating of product gas, wherein, the liquid quenching medium that neutralizes contains alkaline matter, so that the acidity of cohesion and neutralize above-mentioned catalyst fines and/or fine powder.
CN102093153A discloses a kind of purification and the method and apparatus that separates the MTO catalyst fines, wherein, wrap the MTO product gas of stating catalyst fines and/or fine powder and wash and lower the temperature holding under the arm with the method for washing, purifying cooling, thereby above-mentioned catalyst fines and/or fine powder are dammed in washings, realize itself and the separating of MTO product gas.Catalyst fines after quench tower, water wash column washing enters quenched water and washes in the water, and the catalyst fines in the water system can be located deposition at water wash column, water system interchanger, air cooler etc., causes heat exchange efficiency to descend, and influences the device long-term operation.In order to prevent that catalyst fines stops up the equipment that working cycle is flowed through in quenched water and the washing water cycle process, Chinese patent N1942558A discloses a kind of employing one and has overlapped the recovery method of discharging reactor catalyst in one or more hydrocyclone recycle MTO technologies of serial or parallel connection combined running, and catalyzer reclaims use after separating.The conventional solid-liquid cyclone separator or the separation accuracy of wet cyclone are 5-10 μ m, but several vapor-solid cyclonic separation in reactor, have been passed through from the product stream that reactor is discharged, the particle diameter of granules of catalyst is very little, and (particle diameter is 1-20 μ m, 80% grain diameter is below 10 μ m), conventional solid-liquid cyclone separator or wet cyclone can not play effective separating effect.
US2010/0059456A1 discloses a kind of method of using the micro-spin liquid separator to reclaim MTO catalyst fines and/or fine powder from the quenched water of MTO technology and washing water; US7309383B2 discloses a kind of method of using sack cleaner, electrostatic precipitator or strainer to separate conventional gas-solid tripping device, the also separable MTO granules of catalyst of for example cyclonic separator from the MTO product gas of cooling.
Above-mentioned prior art disclosed from MTO product gas the method for separate catalyst fines and/or fine powder realize with wet scrubbing in fast cool zone and washing workshop section mostly, at this moment, these catalyst fines and/or fine powder enter in quench tower and/or the water wash column, can the operation of these equipment be had a negative impact, even these equipment that can wear and tear.Contain acetate in the process water of MTO process, the pH value is between 3.0～6.0 usually; And temperature is higher, generally at 70 ℃～90 ℃.Use the method for wet scrubbing to separate MTO catalyst fines and/or fine powder, catalyzer contacts the skeleton and/or the pore passage structure that can destroy catalyzer with acid wash water, therefore, isolated catalyst fines of wet scrubbing and/or fine powder can't be reused usually.
Although disclosed method has been used sack cleaner in US7309383B2, electrostatic precipitator and/or strainer (525), but owing in reactor (505), do not carry out MTO product gas, water vapour and the first of granules of catalyst separate, therefore, sack cleaner, electrostatic precipitator and/or strainer (525) are isolating not to be catalyst fines and/or fine powder (547), but the thick and/or middle particle of catalyzer (527), catalyst fines and/or fine powder (547) remain in quench tower (550) and are able to realize separating with MTO product gas by wet scrubbing.Therefore, in fact, above-mentioned sack cleaner, electrostatic precipitator and/or strainer (525) have replaced the gas-solid separator of firsts and seconds whirlwind that is usually placed in the reactor (505), it is not to be used to separate grain through common catalyst fines and/or fine powder less than 5 microns, like this, because MTO product gas is entering sack cleaner, electrostatic precipitator and/or strainer (525) will pass through a water cooler (515) before, and realize just that with granules of catalyst isolated M TO product gas is when the water cooler of flowing through (515), the possibility of thick and/or middle particle plugging water cooler of a large amount of catalyzer (515) and pipeline thereof is very big, simultaneously, because the granules of catalyst that MTO product gas carries comprises slightly, in and fine particle and/or fine powder, concentration of solid particles in the product gas is too big, and this also very easily causes sack cleaner, electrostatic precipitator and/or strainer (525) can't works better or obstructions.
Above-mentioned patent documentation is introduced with for referencial use in full at this.
Therefore, so far, to the above-mentioned technical barrier still solution of the reasonable practicality of none.The present invention is devoted to solve above-mentioned technical barrier, and strives finding the practical way that addresses the above problem.
Summary of the invention
According to first aspect present invention, gas-solid separation of a kind of organic oxygen-containing compound system olefin product and heat-exchange system are provided, described system comprises successively:
(1) the gas-solid separator of at least one whirlwind is used for the always described organic oxygen-containing compound system olefin product separating catalyst solid fine particle and/or the fine powder of autoreactor;
(2) at least one interchanger is used to cool off described organic oxygen-containing compound system olefin product, and reclaims heat from product;
(3) at least one strainer is used for from further separating catalyst solid fine particle of described organic oxygen-containing compound system olefin product and/or fine powder;
(4) at least one quench tower is used for the described organic oxygen-containing compound system olefin product of chilling, reclaims heat simultaneously and be used for the alkene separation from product; With
(5) at least one water wash column is used for dividing from described organic oxygen-containing compound system olefin product dried up, reclaims heat simultaneously and be used for alkene and separate from product.
Preferably, described organic oxygen-containing compound is methyl alcohol and/or dme; Described interchanger is the straight tubular heat exchanger of vertical arrangement; Described strainer is ceramic membrane filter device, metal powder sintered filter element strainer and/or electric precipitation strainer.
More preferably, described system comprises at least two strainers in parallel, and one or more strainers and other strainer carry out alternation, most preferably, use is in not one or more strainers of working order from the dry gas blowback of MTO product separating technique demethanizing tower, filters catalyst solid fine particle and/or fine powder in the duct to remove enrichment or to be deposited on described strainer.
Usually, described quench tower is equipped with at least two topping-up pumps, at least two wet cyclones, sewage jar, alkene separation heat exchanging device and air-coolers, wherein, quenching medium in the described quench tower is a water, and a part of catalyst solid fine particle in the described organic oxygen-containing compound system olefin product and/or fine powder enter in the described sewage jar with quenching medium-water; Described water wash column is equipped with topping-up pump, strainer, alkene separation heat exchanging device, watercooler and air-cooler.
Usually, described MTO inside reactor has at least two gas-solid separators of placed in-line whirlwind, is used for the described organic oxygen-containing compound system olefin product initial gross separation catalyst solid particle from inside reactor.
Usually, be mixed in proportion by at least one described strainer and/or the isolating catalyst solid fine particle of the gas-solid separator of at least one described whirlwind and/or fine powder and catalyst activity component-molecular sieve, binding agent, carrier, again pull an oar, behind the spray drying forming, calcination activation, mix with live catalyst or poiser in proportion, formed mixture enters and can be used as live catalyst or poiser use in the described MTO reactor.
According to second aspect present invention, gas-solid separation of a kind of organic oxygen-containing compound system olefin product and heat-exchanging process are provided, comprise successively:
(1) through the gas-solid separator of at least one described whirlwind, always separating catalyst solid fine particle and/or fine powder in the described organic oxygen-containing compound system olefin product of autoreactor;
(2), cool off described organic oxygen-containing compound system olefin product, and from product, reclaim heat through at least one described interchanger;
(3) through at least one described strainer, further separating catalyst solid fine particle and/or fine powder from described organic oxygen-containing compound system olefin product;
(4) through at least one described quench tower, the described organic oxygen-containing compound system olefin product of chilling reclaims heat simultaneously and is used for the alkene separation from product; With
(5) through at least one described water wash column, branch is dried up from described organic oxygen-containing compound system olefin product, reclaims heat simultaneously and be used for the alkene separation from product.
In above-mentioned technology, it is catalyst solid fine particle and/or fine powder more than 1 micron that described strainer can filter out particle diameter usually.
Description of drawings
The Figure of description that constitutes a specification sheets part of the present invention is used for the present invention is further explained; accompanying drawing of the present invention and explanation thereof are used for explaining in detail the present invention; so that those of ordinary skills are expressly understood essence of the present invention more, it does not constitute any restriction to protection domain of the present invention.In the accompanying drawings:
Fig. 1 is the process flow diagram of gas-solid separation of organic oxygen-containing compound system olefin product of the present invention and heat-exchange system.
Embodiment
Be further explained in detail the present invention by description below with reference to accompanying drawing, but following description only is used to make the general technical staff of the technical field of the invention can be expressly understood principle of the present invention and marrow more, and does not mean that the present invention is carried out any type of restriction.Parts that be equal in the accompanying drawing or corresponding or feature are represented with identical reference numerals.
Usually, the some groups of gas-solid separators of in the expanding reach of MTO reactor top, arranging of placed in-line firsts and seconds whirlwind, most granules of catalyst that MTO product gas carries are with after MTO product gas separates, MTO product gas leaves the MTO reactor subsequently and enters three grades of gas-solid separators of whirlwind, and MTO product gas is 800-900mg/m in solid particulate (catalyzer) concentration at the three grades of gas-solid separator inlet of whirlwind places
3, be 150-300mg/m in the concentration of three grades of gas-solid separator outlets of whirlwind
3Therefore, three grades of gas-solid separators of whirlwind can be separated most catalyst fines and/or fine powder, the catalyst fines of separating and/or the size-grade distribution of fine powder are as shown in table 1, catalyst fines and/or fine powder that three grades of gas-solid separators of whirlwind can't be separated enter product separating technique middle and lower reaches workshop section with MTO product gas, this part three grades of gas-solid separator of whirlwind can't isolating catalyst fines and/or the size-grade distribution of fine powder as shown in table 2.
Table 1
Table 2
Usually, there are 62-85 volume % catalyst fines and/or fine powder to be separated in the MTO product gas approximately, but still have quite a few catalyst fines and/or fine powder to enter product separating technique middle and lower reaches workshop section by three grades of gas-solid separators of whirlwind.Especially, as shown in Table 1 and Table 2, it is catalyst fines and/or fine powder below 5 microns that three grades of gas-solid separators of whirlwind can't remove particle diameter.The fine particle and/or the fine powder, about 10% that enter granules of catalyst about 90% that the product gas of product separating technique middle and lower reaches workshop section contains and be particle diameter and be below 5 microns are that particle diameter is the fine particle and/or the fine powder of 5-10 micron.
As shown in Figure 1, MTO is reflected in the reactor 1 and carries out, the catalyzer of inactivation is regenerated in revivifier 2, and get back in the reactor 1 and recycle, reactor 1 and revivifier 2 constitute the MTO reaction-regeneration system, MTO product gas leaves reactor 1 and enters MTO product separating technique section from the top, in the product separating technique section, MTO product gas is earlier after interchanger 4 reclaims heat, enter cooling in the quench tower 6, and washing catalyst fine particle and/or fine powder, at this moment, MTO product gas from bottom to top with quenched water counter current contact under the overhead stream of quench tower 6, the temperature of MTO product gas is reduced by quenched water, simultaneously, its catalyst fines of carrying and/or fine powder are washed out by quenched water.Quenched water divides two strands and is drawn out of at the bottom of the tower of quench tower 6, one quenched water is divided into two-way after the column bottoms pump (unmarked) of quench tower boosts, one the road delivers to the low-temperature heat source of alkene separating unit as alkene separation heat exchanging device 10, to reduce alkene separating unit steam consumption, after quenched water dry type air cooler 11 was cooled to about 60 ℃, agent turned back in the quench tower 6 this road quenched water through returning after the heat exchange as chilling again; Another road directly enters in the slurry tank (not shown) without the quenched water of heat exchange.Another strand quenched water enters after quenched water liquid rotary pump (unmarked) boosts in one-level quenched water wet cyclone 8 and the secondary quenched water wet cyclone 9, remove the catalyst fines and/or the fine powder that carry in the quenched water, the quenched water clear liquid is discharged and is turned back in the quench tower 6 by the top of firsts and seconds wet cyclone 8 and 9, carry all the other quenched waters or the quenched water underflow of catalyst fines and/or fine powder and discharge, and be sent to storage in sewage jar or the sewage lagoon (unmarked) by the bottom of secondary wet cyclone 9.
Usually, no matter adopt which kind of separation method and separating device, MTO product gas can be brought its catalyst fines of carrying of a part and/or fine powder in the above-mentioned quench tower 6 into inevitably, this part catalyst fines and/or fine powder can be washed by quenched water and dam to get off, thereby realization separates with MTO product gas, therefore, a small amount of or appropriate amount of catalysts fine particle and/or fine powder enter in the above-mentioned quench tower 6 and allow, it can not cause too much influence to the operation of quench tower, if but the quantity that enters catalyst fines in the above-mentioned quench tower 6 and/or fine powder is too many, not only can have influence on water wash column 6, quenched water wet cyclone 8 and 9 and various supporting interchanger, the for example operation of air-cooler 11, a certain amount of catalyst fines and/or fine powder also can enter into downstream section water wash column 7 with MTO product gas, thereby have influence on the operation and the operation of water wash column 7, therefore, best bet is that the quantity of the catalyst fines that enters quench tower 6 and/or fine powder is carried out strictness control.
MTO product gas enters the bottom of water wash column 7 by the top of quench tower 6 after quench tower 6 chillings coolings, be provided with the several layers tower tray in the conventional water wash column, is provided with the oil removal facility at the bottom of the tower.MTO product gas from bottom to top with the washing water counter current contact of getting off from water wash column 7 overhead stream, thereby further reduce the temperature of MTO product gas, and the water in the MTO product gas removed, washing water is extracted out at the bottom of the tower of water wash column 7, after boosting, the column bottoms pump (unmarked) of water wash column is divided into two strands, one enters washing water filter (not shown), remove by filter the catalyst fines and/or the fine powder that carry in the washing water, and with from one of the MTO product air compressor of olefin separation, two, the washing water (not shown) of three sections phlegma (not shown) and alkene separating unit mixes, and enters afterwards in the slurry tank (not shown).Another burst washing water is sent in the bottom reboiler (not shown) of propylene rectification tower of alkene separating unit the thermal source as alkene separation heat exchanging device 10, this one washing water heat exchange again is divided into two-way with washing after watercooler 12 is cooled to 55 ℃ after wash water dry type air cooler 11, one the tunnel enters in the middle part tower tray of water wash column 7, another road enters in the top tower tray of water wash column 7 after washing watercooler 12 is cooled to 37 ℃.After extracting out, petrol-feed pump (not shown) at the bottom of the tower of water wash column 7 delivers to the alkene separating unit by the isolated small quantities of gasoline of oil removal facility at the bottom of the tower.
If excessive catalyst fines and/or fine powder enter in the water wash column 7, these catalyst fines and/or fine powder not only can remain in the washing water, also can remain in by in the isolated small quantities of gasoline of oil removal facility at the bottom of the tower.Catalyst fines in the water system can be located deposition at water wash column, water system interchanger, air cooler etc., causes heat exchange efficiency to descend, and influences the device long-term operation.But the catalyst fines and/or the fine powder that remain in the gasoline that above-mentioned condensation gets off can't separate or remove; like this; the gasoline of good fluidity will become the slurry wax of poor flow quality; itself or increase the load or the blocking pipe of pump, thereby cause system's operation undesired or stop.This is that control enters one of catalyst fines in the water wash column 7 and/or reason of fine powder quantity.
In system's normal operation process, because three grades of gas-solid separators 3 of whirlwind can't remove catalyst fines below 5 microns and/or fine powder, so, these catalyst fines and/or fine powder will be with MTO product gas successively by interchanger 4, quench tower 6, water wash column 7, the tower bottom reboiler (not shown) of alkene knockout tower, quenched water air-cooler 11, the tower bottom reboiler (not shown) of propylene rectification tower, washing water dry type air cooler 11, washing watercooler 12 devices such as grade, along with system's prolongation of runtime, above-mentioned catalyst fines in the MTO product gas and/or fine powder will enrichments gradually in said apparatus, can cause the tower tray of water wash column 7 to stop up when serious; Catalyst fines and/or fine powder are accumulated in the tower bottom reboiler (not shown) of washing water air cooled heat exchanger 11, water cooling interchanger 12, alkene knockout tower etc. and locate, thereby cause system's heat exchange efficiency to reduce, need regularly aforesaid device be cleared up and safeguard, so just reduced production efficiency, increased labour intensity.
The present invention proposes first in the methanol to olefins reaction system of pressurization, 4(is used for the heating methanol raw material at MTO product gas interchanger) outlet and the inlet of quench tower 6 between at least one strainer 5 is set, to remove trace catalyst fine particle and/or the fine powder that carries in the MTO product gas, these catalyst fines and/or fine powder are filtered device 5 and are retained down, the catalyst fines in the MTO product gas and/or the quantity of fine powder will significantly reduce, this can reduce to a great extent with MTO product gas and enters the catalyst fines of product gas separating technology middle and lower reaches workshop section and/or the quantity of fine powder, thereby prevents quench tower 6, water wash column 7, quenched water wet cyclone 8 and 9 and the reduction of various interchanger working efficiencies, and prevent that system operation is unusual.
Usually, MTO product gas temperature after straight tubular heat exchanger 4 heat exchange of vertical arrangement can be reduced to about 270-340 ℃ from 480 ℃, so, the operational condition of above-mentioned strainer 5 is comparatively gentle, with between the interchanger 4 of the outlet of three grades of gas-solid separators 3 of whirlwind of system and MTO product gas and methanol feedstock, strainer is set and compares, facility investment is lower, and it is easier to operate.
Usually, the preferred strainer 5 that uses is strainers such as ceramic membrane filter, metal powder sintered core strainer and/or electric precipitator among the present invention, but does not also get rid of any strainer that is applicable to other type of the object of the invention.
With the porcelain filter is example, strainer can comprise: filter supporting body, filter body and strainer web member, wherein, filter body employing aperture is 10 microns a ceramic membrane, it is fairshaped hollow drum shape, wall thickness can be 4～5mm, and the filter body below is provided with supporter, and the top is provided with web member.MTO product gas is from the internal space that the side surface or the perimeter surface of the filter body of round barrel shape enters filter body, and leaving described strainer from the top, internal space of filter body, wherein most particle diameters are intercepted at the strainer outside greater than 1 micron catalyst solid fine particle and/or fine powder.
Strainer of the present invention also can use with the strainer of metal powder sintered filter element as filter element, for example, adopt Stainless Steel Powder or metallic titanium powder sintered filter core, it is to be raw material with Stainless Steel Powder or metallic titanium powder, a kind of new and effective porous filter material that technological processs such as process powder classification, moulding, sintering, mechanical welding processing are made, its internal void curved configuration, crisscross, even aperture distribution, hole and filtering accuracy can be adjusted in quite wide scope, and filtration mechanism is typical Depth Filtration.
Usually, the filtering accuracy of porcelain filter that the present invention uses or metal powder sintered filter element strainer is the 1-2 micron, is preferably 1 micron.
That porcelain filter or metal powder sintered filter element strainer have is corrosion-resistant, high temperature resistant, intensity is big, filtering accuracy guarantees easily and easy excellent properties such as regeneration.Their aerial use temperatures can reach 500～600 ℃, and have good mechanical property, even work under High Temperature High Pressure, the aperture can not deform yet, and porosity can be up to 35～45%, even aperture distribution, pollutant holding capability is big, and renovation process is simple, and the regeneration back is reusable.
Preferably, in the present invention, the working pressure of methanol to olefins reaction is 0.2～0.5Mpa.After MTO product gas and the methanol feedstock heat exchange, temperature is reduced to about 270-340 ℃, enters in the above-mentioned strainer 5 again and filters, to remove particle diameter greater than 1 micron catalyst solid fine particle and/or fine powder.
Preferably, system of the present invention comprises at least two in parallel strainers, and one or more strainer and other strainer carry out alternation, promptly adopts a part of strainer work, the stand-by alternate mode of another part strainer.When the filter pressure drop of operation increases fast, stand-by strainer is switched in the working order, and be in that part of strainer stand-by or not working order with pressurized air or from the dry gas blowback of MTO product separating technique demethanizing tower, filter catalyst solid fine particle and/or fine powder in the duct to remove enrichment or to be deposited on described strainer.
System of the present invention and technology thereof can avoid in the MTO product gas contained catalyst solid fine particle and/or fine powder to enter in a large number in quench tower 6 and the water wash column 7 in chilling and washing treating processes, at the bottom of causing quench tower 6 towers, water wash column 7 tower trays and various interchanger stop up, avoid because above-mentioned obstruction causes the device operational anomaly, thereby reduce equipment cleaning running cost and labour intensity.
The invention step of system of the present invention and technology thereof not only be to use strainer 5 replace wet scrubbing method of the prior art remove the gas-solid separator of conventional 1-3 level whirlwind can't isolating particle diameter at catalyst fines below 5 microns and/or fine powder, more be on the proper work sections link to be provided with or increase at least one strainer 5 interception and separate above-mentioned catalyst fines and/or fine powder, make promptly type to above-mentioned strainer 5, material is selected and operational requirement can be not too high, make that again filtration efficiency is very good, therefore, technology of the present invention and method also show advantage that following prior art is beyond one's reach at least except foregoing advantage.
By the gas-solid separator 3 of 3 grades of whirlwind of the present invention and/or strainer 5 isolating catalyst fines and/or fine powder owing to be collected before MTO product gas enters quench tower 7, therefore, it is the same with the isolating granules of catalyst of the gas-solid separator of 1-2 level whirlwind in being located at MTO reactor 1, be dry and without water logging bubble and erosive, therefore, gas-solid separator 3 of 3 grades of whirlwind of the present invention and/or strainer 5 isolating catalyst fines and/or fine powder can be mixed in proportion postactivated with the isolating granules of catalyst of the gas-solid separator of 1-2 level whirlwind that is located in the MTO reactor 1, or be mixed in proportion after the activation, formed mixture can enter in the MTO reactor 1, uses as fresh or regenerated catalyst; Or can be mixed in proportion with live catalyst after the gas-solid separator 3 of 3 grades of whirlwind of the present invention and/or strainer 5 isolating catalyst fines and/or the fine powder activation, formed mixture can enter in the MTO reactor 1, uses as fresh or regenerated catalyst.And catalyst fines that wet scrubbing is separated and/or fine powder be owing to be subjected to water logging bubble and corrode, and catalyst backbone caves in, the inner duct of catalyzer destroys, and therefore, it can't be reused as catalyzer once more.
Because the strainer 5 of system of the present invention and technology is located at the interchanger 4 and the MTO product gas of MTO product gas and methanol feedstock and enters between the inlet of quench tower 6, at this moment, the temperature of MTO product gas is reduced to 270-340 ℃ from 480 ℃, therefore, the temperature and pressure situation of MTO product gas can be to the type of strainer 5, material is selected and operational condition proposes excessive demand, the operational condition of strainer 5 is comparatively gentle, feasible filtration is easier to realize, if but strainer 5 is located between the interchanger 4 of 3 grades of gas-solid separators 3 of whirlwind and MTO product gas and methanol feedstock, or be located between the inlet of the outlet of MTO reactor 1 and 3 grades of gas-solid separators 3 of whirlwind, then situation will become greatly, because, at this moment, the temperature of MTO product gas up to 480 ℃ about, certainly will be to the type of strainer 5, material is selected and operational condition proposes excessive demand.
Certainly, theoretically, above-mentioned strainer 5 also can be located between the MTO product gas inlet of the MTO product gas outlet of quench tower 6 and water wash column 7, but this moment, a catalyst fines and/or a fine powder part that MTO product gas carries enter water system with quenched water, soak through quenched water, as previously mentioned, collected like this catalyst fines and/or fine powder can't be reused as catalyzer once more; The part catalyst fines and/or the fine powder utmost point are still in the product air-flow, the quench tower Outlet Gas Temperature is about 110 ℃, fluctuation appears as the quench tower service temperature, the water condensation that contains in the product gas gets off, the easy filtration duct of blocking filter, cause strainer can't works better or filtration efficiency obviously descend.
Therefore, in system of the present invention and technology, determine the position of strainer in total system and that strainer itself is set is the same, most important for the realization of the object of the invention, the two is in conjunction with constituting invention step of the present invention.
So the strainer that is provided with makes that filtration condition promptly is easier to reach, make that again filter effect is very good, usually, strainer of the present invention can filter out particle diameter more than 80% at catalyst fines and/or fine powder more than 1 micron and below 5 microns, thereby makes that the quantity that enters catalyst fines in MTO product gas separating technology middle and lower reaches workshop section, for example quench tower and/or the water wash column and/or fine powder is considerably less.
Explain the present invention in further detail below by exemplary and nonrestrictive specific embodiment, so that those of ordinary skills are expressly understood essence of the present invention and marrow more.
Embodiment
Use system of the present invention shown in Figure 1 1,800,000 tons of/year methanol-to-olefins products to be carried out gas-solid the separation and heat exchange with technology.The processing parameter that system adopted is shown in following table 3.
Table 3
The Al that is adopted
2O
3The structural parameter of ceramic membrane filter device and operational condition are shown in following table 4:
Table 4
From table 3 and table 4, find out: in system of the present invention and technology, the filtration efficiency of strainer is up to 80%, it effectively separates and has held back the gas-solid separator of 1-3 level whirlwind can't catalyst fines and/or the fine powder of isolating particle diameter between the 1-5 micron, alleviate the segregational load of MTO product gas separating technology middle and lower reaches workshop sections greatly, avoided the problem of MTO product gas separating technology middle and lower reaches workshop section equipment operation exception.
Term that this specification sheets is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that will represent and describe unintentionally when using these terms and form of presentation or any equivalent exclusion of its integral part.
Although represented and described several embodiments of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize under the situation that does not break away from principle of the present invention and spirit can carry out any accommodation and improvement to these embodiments, and protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (13)
1. gas-solid separation of organic oxygen-containing compound system olefin product and heat-exchange system comprise successively:
(1) the gas-solid separator of at least one whirlwind is used for from described organic oxygen-containing compound system olefin product separating catalyst solid fine particle and/or fine powder from the MTO reactor;
(2) at least one interchanger is used to cool off described organic oxygen-containing compound system olefin product, and reclaims heat from product;
(3) at least one strainer is used for from further separating catalyst solid fine particle of described organic oxygen-containing compound system olefin product and/or fine powder;
(4) at least one quench tower is used for the described organic oxygen-containing compound system olefin product of chilling, reclaims heat simultaneously and be used for the alkene separation from product; With
(5) at least one water wash column is used for dividing from described organic oxygen-containing compound system olefin product dried up, reclaims heat simultaneously and be used for alkene and separate from product.
2. system according to claim 1, wherein, described organic oxygen-containing compound is methyl alcohol and/or dme.
3. system according to claim 1, wherein, described interchanger is the straight tubular heat exchanger of vertical arrangement.
4. system according to claim 1, wherein, described strainer is ceramic membrane filter device, metal powder sintered filter element strainer and/or electric precipitation strainer.
5. system according to claim 4, described system comprise at least two in parallel strainers, and one or more strainer and other strainer carry out alternation.
6. system according to claim 5, wherein, use is in not one or more strainers of working order from the dry gas blowback of MTO product separating technique demethanizing tower, filters catalyst solid fine particle and/or fine powder in the duct to remove enrichment or to be deposited on described strainer.
7. system according to claim 1, wherein, described quench tower is equipped with at least two topping-up pumps, at least two wet cyclones, sewage jar, alkene separation heat exchanging device and air-coolers.
8. system according to claim 7, wherein, the quenching medium in the described quench tower is a water, a part of catalyst solid fine particle and/or fine powder in the described organic oxygen-containing compound system olefin product enter in the described sewage jar with quenching medium-water.
9. system according to claim 1, wherein, described water wash column is equipped with topping-up pump, strainer, alkene separation heat exchanging device, watercooler and air-cooler.
10. system according to claim 1, wherein, described MTO inside reactor has at least two gas-solid separators of placed in-line whirlwind, is used for the described organic oxygen-containing compound system olefin product initial gross separation catalyst solid particle from inside reactor.
11. according to claim 1 or the described system of claim 10, wherein, be mixed in proportion by at least one described strainer and/or the isolating catalyst solid fine particle of the gas-solid separator of at least one described whirlwind and/or fine powder and catalyst activity component-molecular sieve, binding agent, carrier, again pull an oar, behind the spray drying forming, calcination activation, mix with live catalyst or poiser in proportion, formed mixture enters in the described MTO reactor and uses as live catalyst or poiser.
12. gas-solid separation of organic oxygen-containing compound system olefin product and heat-exchanging process comprise successively:
(1) through the gas-solid separator of at least one described whirlwind, always separating catalyst solid fine particle and/or fine powder in the described organic oxygen-containing compound system olefin product of autoreactor;
(2), cool off described organic oxygen-containing compound system olefin product, and from product, reclaim heat through at least one described interchanger;
(3) through at least one described strainer, further separating catalyst solid fine particle and/or fine powder from described organic oxygen-containing compound system olefin product;
(4) through at least one described quench tower, the described organic oxygen-containing compound system olefin product of chilling reclaims heat simultaneously and is used for the alkene separation from product; With
(5) through at least one described water wash column, branch is dried up from described organic oxygen-containing compound system olefin product, reclaims heat simultaneously and be used for the alkene separation from product.
13. it is catalyst solid fine particle and/or fine powder more than 1 micron that technology according to claim 12, wherein said strainer filter out particle diameter.
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Application publication date: 20130724 |