CN103524286A - Methanol and C4-to-olefin quenched water and washing water airtight coupling treatment method and device - Google Patents
Methanol and C4-to-olefin quenched water and washing water airtight coupling treatment method and device Download PDFInfo
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- CN103524286A CN103524286A CN201310496440.6A CN201310496440A CN103524286A CN 103524286 A CN103524286 A CN 103524286A CN 201310496440 A CN201310496440 A CN 201310496440A CN 103524286 A CN103524286 A CN 103524286A
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- quenched
- reaction gas
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 203
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nODVweCcgaGVpZ2h0PSc4NXB4JyB2aWV3Qm94PScwIDAgODUgODUnPgo8IS0tIEVORCBPRiBIRUFERVIgLS0+CjxyZWN0IHN0eWxlPSdvcGFjaXR5OjEuMDtmaWxsOiNGRkZGRkY7c3Ryb2tlOm5vbmUnIHdpZHRoPSc4NS4wJyBoZWlnaHQ9Jzg1LjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8cGF0aCBjbGFzcz0nYm9uZC0wIGF0b20tMCBhdG9tLTEnIGQ9J00gNTEuMyw0Mi4wIEwgMjcuMyw0Mi4wJyBzdHlsZT0nZmlsbDpub25lO2ZpbGwtcnVsZTpldmVub2RkO3N0cm9rZTojRTg0MjM1O3N0cm9rZS13aWR0aDoxLjBweDtzdHJva2UtbGluZWNhcDpidXR0O3N0cm9rZS1saW5lam9pbjptaXRlcjtzdHJva2Utb3BhY2l0eToxJyAvPgo8cGF0aCBjbGFzcz0nYm9uZC0wIGF0b20tMCBhdG9tLTEnIGQ9J00gMjcuMyw0Mi4wIEwgMy40LDQyLjAnIHN0eWxlPSdmaWxsOm5vbmU7ZmlsbC1ydWxlOmV2ZW5vZGQ7c3Ryb2tlOiMzQjQxNDM7c3Ryb2tlLXdpZHRoOjEuMHB4O3N0cm9rZS1saW5lY2FwOmJ1dHQ7c3Ryb2tlLWxpbmVqb2luOm1pdGVyO3N0cm9rZS1vcGFjaXR5OjEnIC8+Cjx0ZXh0IHg9JzUyLjcnIHk9JzUzLjInIGNsYXNzPSdhdG9tLTAnIHN0eWxlPSdmb250LXNpemU6MjJweDtmb250LXN0eWxlOm5vcm1hbDtmb250LXdlaWdodDpub3JtYWw7ZmlsbC1vcGFjaXR5OjE7c3Ryb2tlOm5vbmU7Zm9udC1mYW1pbHk6c2Fucy1zZXJpZjt0ZXh0LWFuY2hvcjpzdGFydDtmaWxsOiNFODQyMzUnID5PPC90ZXh0Pgo8dGV4dCB4PSc2OC4yJyB5PSc1My4yJyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjIycHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojRTg0MjM1JyA+SDwvdGV4dD4KPC9zdmc+Cg== OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000005406 washing Methods 0.000 title claims abstract description 83
- 230000001808 coupling Effects 0.000 title claims abstract description 16
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 16
- 238000010791 quenching Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 41
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000000746 purification Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 239000012495 reaction gas Substances 0.000 claims description 76
- 150000001336 alkenes Chemical class 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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- 125000004805 propylene group Chemical group 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[H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a methanol and C4-to-olefin quenched water and washing water airtight coupling treatment method and device. The methanol and C4-to-olefin quenched water and washing water airtight coupling treatment method provided by the invention comprises the following steps: (a) carrying out rotational flow purification on reaction gases on the tops of a quenching tower and a C4 quenching tower so as to remove catalyst particles and liquid hydrocarbon entrained in the reaction gases, and washing the purified reaction gases by using water so as to improve the quality of the washing water; (b) carrying out liquid-solid separation and concentration on quenched water containing catalyst particles at the bottoms of the quenching tower and the C4 quenching tower, carrying out heat exchange on the separated and purified quenched water, and then returning the quenched water to the quenching tower so as to recycle the quenched water; (c) carrying out drying treatment on the separated and concentrated catalyst, and recycling the catalyst particles; (d) carrying out rotational flow oil removal on the washing water serving as feedstock of a stripping tower, purifying the washing water, and recycling sump oil entrained in the washing water, so that the quality of the water purified by the stripping tower reaches the standard. The invention also provides the methanol and C4-to-olefin quenched water and washing water airtight coupling treatment device.
Description
Technical field
The invention belongs to coal transformation technology field, relate to a kind of catalyzer in the quenched water that micro-cyclone separator recycles methyl alcohol and carbon four alkene processed, method of the sump oil in Separation of Water wash water of adopting.Specifically, the present invention relates to a kind of methyl alcohol and the quenched water of carbon four alkene processed and the method and apparatus of the airtight coupling processing of washing water.
Background technology
Ethene and propylene are as two kinds of important basic chemical industry raw materials, and its demand constantly increases in recent years.Day by day in short supply along with petroleum resources, the production line that the oil of originally take is raw material be take gradually the production line that coal, Sweet natural gas, biomass etc. are raw material and is replaced.By coal, Sweet natural gas, biomass equal energy source, made the oxygenatedchemicalss such as alcohols, ethers, ester class, then replace oil to produce light olefin by these oxygenatedchemicalss.Nowadays, some oxygenatedchemicalss can reach fairly large production, as methyl alcohol, can be made by coal or Sweet natural gas, and technique is very ripe, can realize the industrial scale of up to a million tonnes.Popularity due to oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.In MTO technique, in order to improve olefin yields, methyl alcohol and additive enter reactor reaction after preheating, reacted reaction gas (I) carries out heat exchange through quench tower and water wash column, washing, following reaction gas enters depropanizing tower via compressor compresses, low-carbon alkene enters olefin separation, and by product carbon four and above alkene enter again C 4 reaction device and carry out cracking and generate low-carbon alkene after separation, the reaction gas (II) generating from C 4 reaction device carries out heat exchange through quench tower and water wash column, washing rear two strands of quenched waters converges through two-stage eddy flow concentrated and dry, after the quenched water heat exchange purifying, as chilling, quench tower is returned in agent, the dry catalyzer obtaining can reuse.
For oxygenatedchemicals, be converted into the technique of alkene, US0234281 has proposed after application vapor-solid cyclonic separation separating reaction discharging current, and granules of catalyst is recycled in recycling wet scrubbing and non-essential drying zone.But under nominal situation, in methanol-to-olefins chilling waste water, the catalyst particles of 80% left and right is all less than 5 microns, and advanced cyclonic separator can only be removed 5 microns of above particles, be difficult to meet operating mode demand, and this method also can cause quenched water to recycle rate declining to a great extent, and produce a large amount of efflux wastewaters.
Chinese invention patent application CN101352620A discloses the micro-cyclone concentrating method of trickle catalyzer in a kind of MTO quenched water, washing water, utilize micro-swirler concentrate 2 microns of following granules of catalyst after at the bottom of raising quench tower in water catalyst content more a part of catalyzer is discharged with quenched water.But in order to improve yield of light olefins, in novel process, reaction gas output is more much larger than originally, and the catalyst content of carrying secretly accordingly also increases a lot.The method can not meet containing the technique of a large amount of granules of catalyst and can cause catalyst attrition excessive.
Therefore, in order to meet, this by carbon four and above alkene, scission reaction is to improve the MTO novel process of olefin yields again, and a kind of novel method that can airtight coupling processing MTO reaction waste of exploitation is badly in need of in this area.
Summary of the invention
The invention provides a kind of methyl alcohol of novelty and the quenched water of carbon four alkene processed and the airtight coupled processing method of washing water and device, solved the processing problem of quenched water and washing water in existing methyl alcohol and carbon four olefin process processed.
On the one hand, the invention provides quenched water and the airtight coupled processing method of washing water of a kind of methyl alcohol and carbon four alkene processed, the method comprises the following steps:
(a) reaction gas of chilling tower top, C4 chilling tower top is carried out to eddy flow purification, catalyst particles and the liquid hydrocarbon to remove reaction gas, carried secretly; Reaction gas after purifying is washed, to realize the improvement of washing water water quality;
(b) quenched water containing catalyst particles at the bottom of quench tower, at the bottom of C4 quench tower is carried out to liquid-solid separation and concentrated, the quenched water after isolation of purified returns to quench tower after heat exchange, to realize the recycle of quenched water;
(c) catalyzer after separated and concentrated is carried out to drying treatment, reclaim catalyst particles; And
(d) washing water as stripping tower charging is carried out to cyclone deoiling, to its purification and reclaim the sump oil that it is carried secretly, to realize stripping tower the up to standard of water quality of purifying waste water.
One preferred embodiment in, described in carry out the reaction gas of eddy flow purification oleaginousness be 1500-3000mg/L, catalyst content is 200-500mg/L.
Another preferred embodiment in, after eddy flow purifies, the oleaginousness of reaction gas is down in 250mg/L, catalyst content is down in 60mg/L.
Another preferred embodiment in, the working temperature of the described quenched water containing catalyst particles is 85-115 ℃, density is 900-930kg/m
3, catalyst particle size is 1-20 micron, the water-filling density of catalyzer is 1200-1600kg/m
3.
Another preferred embodiment in, the catalyst particles content of the described quenched water containing catalyst particles is 600-1100mg/L.
Another preferred embodiment in, liquid-solid separation and concentrated after, the catalyst particles content of quenched water is down in 100mg/L, the rich catalyst pulp inner catalyst of underflow content reach 40g/L or higher more than; Liquid-solid separation accuracy is 1 μ m.
Another preferred embodiment in, the efficiency of described cyclone deoiling reaches 85% or higher, the oil-contg of stripping tower in purifying waste water is not more than 20ppm.
On the other hand, the invention provides quenched water and the washing water coupling processing device of a kind of methyl alcohol and carbon four alkene processed, this device comprises:
Be placed in respectively reaction gas cyclone purifier, the C4 reaction gas cyclone purifier at quench tower, C4 quench tower top, for the reaction gas of chilling tower top, C4 chilling tower top being carried out to eddy flow purification, catalyst particles and the liquid hydrocarbon carried secretly to remove reaction gas;
The water wash column, the C4 water wash column that are connected with the top of quench tower, C4 quench tower respectively, for the reaction gas after purifying is washed, to realize the improvement of washing water water quality;
The micro-cyclone clarificator and the micro-swirl concentrator that are connected in series with the bottom of quench tower, C4 quench tower, for the quenched water containing catalyst particles at the bottom of quench tower, at the bottom of C4 quench tower, carry out liquid-solid separation and concentrated, quenched water after isolation of purified returns to quench tower after heat exchange, to realize the recycle of quenched water;
Be connected with the bottom of micro-swirl concentrator from returning charge blade dryer, for the catalyzer to after separated and concentrated, carry out drying treatment, reclaim catalyst particles; And
The washing water degreaser cyclone, the C4 washing water degreaser cyclone that are connected with the bottom of water wash column, C4 water wash column respectively, for the washing water as stripping tower charging is carried out to cyclone deoiling, to its purification and reclaim the sump oil that it is carried secretly, to realize stripping tower the up to standard of water quality of purifying waste water.
One preferred embodiment in, described reaction gas cyclone purifier, C4 reaction gas cyclone purifier, micro-cyclone clarificator, micro-swirl concentrator, washing water degreaser cyclone and C4 washing water degreaser cyclone are composed in parallel by single or many eddy flow core pipes.
Another preferred embodiment in, the pressure-losses of described reaction gas cyclone purifier, C4 reaction gas cyclone purifier, micro-cyclone clarificator, micro-swirl concentrator, washing water degreaser cyclone and C4 washing water degreaser cyclone is 0.15-0.25MPa.
Accompanying drawing explanation
According to carrying out following detailed description by reference to the accompanying drawings, it is more obvious that object of the present invention and feature will become, in accompanying drawing:
Fig. 1 is according to the processing technological flow figure of the methyl alcohol of an embodiment of the invention and carbon four alkene quenched water processed and washing water.
Embodiment
Present inventor is through finding after extensive research, by specific technique, quenched water and the washing water of the carbon four cracking alkene in the quenched water of methanol-to-olefins and washing water, methanol-to-olefins by product are combined to airtight coupling processing, can so that reaction water, quenched water and the washing water of methyl alcohol and carbon four alkene processed all recycle; Reaction used heat has also obtained reclaiming to greatest extent; The catalyzer reclaiming can reuse, and has reduced production cost, has extended device running period, two strands of quenched waters converge share a set of cyclone clarification afterwards, concentrated and drying plant is processed, and has also reduced cost of equipment when having reduced occupation area of equipment.Based on above-mentioned discovery, the present invention is accomplished.
In a first aspect of the present invention, quenched water and the airtight coupled processing method of washing water of a kind of methyl alcohol and carbon four alkene processed is provided, the method comprises the following steps:
(i) the reaction gas of chilling tower top, C4 chilling tower top is carried out to eddy flow purification, remove catalyst particles and liquid hydrocarbon that reaction gas is carried secretly, the reaction gas after purification removes water wash column, to realize the improvement of washing water water quality;
(ii) the quenched water containing catalyst particles at the bottom of quench tower, at the bottom of C4 quench tower is carried out to liquid-solid separation, concentrated, the quenched water after isolation of purified returns to quench tower as quenched water after heat exchange, to realize the recycle of quenched water;
(iii) the catalyzer after separated, concentrated is carried out to drying treatment, reclaim catalyst particles; And
(iv) stripping tower charging is carried out to cyclone deoiling, purify stripping tower charging and also reclaim the sump oil that it is carried secretly, to realize stripping tower the up to standard of water quality of purifying waste water.
In the present invention, the oleaginousness that enters the reaction gas of chilling tower top cyclone purifier is reduced in 200mg/L by 2500mg/L, and catalyst content is reduced in 60mg/L by 200-500mg/L.
In the present invention, the working temperature of described MTO quenched water is 85-115 ℃, and density is 900-930kg/m
3, catalyst particle size is 1-20 micron, the water-filling density of catalyzer is 1200-1600kg/m
3.
In the present invention, at the bottom of described quench tower, recirculated water is reduced to below 100mg/L by original 1000mg/L by the catalyst content of micro-cyclone clarificator and thickener, more than the rich catalyst pulp inner catalyst of underflow content can reach 40g/L, separation accuracy is about 1 μ m.
In the present invention, described cyclone deoiling efficiency reaches more than 85%, and the oil-contg of air lift in purifying waste water is not more than 20ppm.
In a second aspect of the present invention, quenched water and the washing water coupling processing device of a kind of methyl alcohol and carbon four alkene processed is provided, this device comprises:
Be placed in quench tower top, for reaction gas is carried out to micro-cyclonic separation, to remove the reaction gas cyclone purifier of wherein contained liquid hydrocarbon and catalyzer;
Be connected in series with the bottom of quench tower, catalyzer in water at the bottom of MTO quench tower is carried out to two-stage eddy flow successively concentrated-dry, to obtain micro-cyclone clarificator of dry catalyzer and clean quench circulation water, micro-swirl concentrator and from returning charge blade dryer; And
Be connected with the bottom of water wash column, in order to remove the washing water degreaser cyclone of the sump oil in MTO washing water.
In the present invention, described reaction gas cyclone purifier, micro-cyclone clarificator, micro-swirl concentrator and washing water degreaser cyclone are composed in parallel by single, two or more eddy flow core pipes.
In the present invention, the pressure-losses of described reaction gas cyclone purifier, micro-cyclone clarificator, micro-swirl concentrator and washing water degreaser cyclone is 0.15-0.25MPa.
Below describe with reference to the accompanying drawings apparatus structure of the present invention and method in detail.
Fig. 1 is according to the processing technological flow figure of the methyl alcohol of an embodiment of the invention and carbon four alkene quenched water processed and washing water.As shown in Figure 1:
Methyl alcohol and additive enter reactor 2 reactions after preheater 1 preheating, it is cooling that the reaction gas generating and by product enter quench tower 4 by reactor 2 tops, reaction gas after reaction gas cyclone purifier 5 eddy flows of quench tower 4 tower tops purify enters water wash column 6 by reaction gas cyclone purifier 5 tops, and catalyst particles is stayed quench tower 4 bottoms; Reaction gas, after washing, enters depropanizing tower 10 by water wash column 6 tops after compressor 9 compressions, and the following alkene of C4 enters subsequent processing and removes separation of olefins, and in order to improve product yield, C4 and above alkene return to C4 reactor 12 and again carries out scission reaction; The washing water of water wash column 6 bottoms after the 8 degreaser cyclone separation of washing water degreaser cyclone, oil recovery, washing water up to standard removes stripping tower;
The reaction gas that the C4 of take obtains as raw material with take methyl alcohol as the reaction gas that raw material obtains the same, it is cooling that the reaction gas that C4 reactor 12 generates and by product enter C4 quench tower 13 by C4 reactor 12 tops, reaction gas after C4 reaction gas cyclone purifier 14 eddy flows of quench tower 13 tower tops purify enters C4 water wash column 15 by the top of C4 reaction gas cyclone purifier 14, and catalyst particles is stayed C4 quench tower 13 bottoms; Reaction gas, after washing, enters C4 depropanizing tower 18 by C4 water wash column 15 tops after 17 compressions of C4 compressor, and the following alkene of C4 enters subsequent processing and removes separation of olefins; The washing water of C4 water wash column 15 bottoms after the 16 degreaser cyclone separation of C4 washing water degreaser cyclone, oil recovery, washing water up to standard removes stripping tower;
At the bottom of C4 quench tower 13 towers, at the bottom of quenched water and methanol-to-olefins quench tower 4 towers, quenched water passes through micro-cyclone clarificator 7-1 and micro-swirl concentrator 7-2 successively after converging, the quenched water of clarification after heat exchange as chilling agent return to quench tower 4 and C4 quench tower 13; The concentrated catalyst pulp obtaining through reclaiming catalyzer utilization after returning charge blade drier 19 is dry;
The product of reactor 2 bottoms and air together enter revivifier 3 regeneration, and the product of regeneration together enters 11 regeneration of C4 revivifier, the CO of generation, CO by revivifier 3 tops and air
2deng gas, by C4 revivifier 11 tops, discharged; The product circulation that discharge revivifier 3 bottoms enters reactor 2; The product circulation that discharge C4 revivifier 11 bottoms enters C4 reactor 12; The product of C4 reactor 12 bottoms and air together circulate and enter 11 regeneration of C4 revivifier.
Major advantage of the present invention is:
1) quenched water of methyl alcohol of the present invention and carbon four alkene processed and the airtight coupling processing device of washing water, adopt successively the micro-cyclone separator of solution-air to carry out eddy flow purification to chilling tower top reaction gas, granules of catalyst at the bottom of adopting liquid-solid micro-cyclone separator to quench tower in quenched water carries out separation, concentrates and recycle after drying and adopt the micro-cyclone separator of liquid-liquid to carry out cyclone deoiling to stripping tower charging, purify stripping tower charging and also reclaim the sump oil that it is carried secretly, to realize stripping tower the up to standard of water quality of purifying waste water.
2) quenched water of methyl alcohol of the present invention and carbon four alkene processed and the airtight coupled processing method of washing water, dexterously in conjunction with multiple micro-cyclone separator, quenched water and washing water in methyl alcohol and carbon four olefine reaction processed are carried out to airtight coupling processing, by the isolation of purified to chilling tower top reaction gas, guarantee that the granules of catalyst entering in quench tower with reaction gas is not brought into water wash column; By the separation of the granules of catalyst in quenched water at the bottom of quench tower, concentrated and dried recovered, at the bottom of having reduced production cost and having made quench tower, granules of catalyst concentration keeps a running balance, quenched water carries out entering interchanger after separation to catalyzer by cyclone clarificator again, can avoid granules of catalyst to enter interchanger, stop up interchanger or reduce heat exchange efficiency; To entering the sewage of stripping tower, carry out cyclone deoiling, guarantee that stripping tower charging is up to standard.
3) quenched water of methyl alcohol of the present invention and carbon four alkene processed and the airtight coupled processing method of washing water, by two strands of quenched waters are converged, share a set of cyclone clarification afterwards, concentrated and drying plant is processed, not only reduced occupation area of equipment but also reduced cost of equipment.
4) quenched water of methyl alcohol of the present invention and carbon four alkene processed and the airtight coupled processing method of washing water and device make the reaction waste that produces in methyl alcohol and carbon four olefins reaction process processed and quenched water, the whole hermetic reclaim utilizations of washing water, reaction used heat is utilized, the catalyzer reclaiming can be reused, reduced production cost, extended device running period, reduce cost of equipment simultaneously, reduced occupation area of equipment.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.But, should be understood that these embodiment only do not form limitation of the scope of the invention for the present invention is described.The test method of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all per-cent and umber are by weight.
embodiment 1:
In 600,000 tons/year of olefin process processes of 1,800,000 tons/year of Methanols, according to method of the present invention, adopt quenched water and the airtight coupling processing device of washing water of methyl alcohol and carbon four alkene processed, (1) reaction gas of chilling tower top, C4 chilling tower top is carried out to eddy flow purification, catalyst particles and the liquid hydrocarbon to remove reaction gas, carried secretly; Reaction gas after purifying is washed, to realize the improvement of washing water water quality; (2) quenched water containing catalyst particles at the bottom of quench tower, at the bottom of C4 quench tower is carried out to liquid-solid separation and concentrated, the quenched water after isolation of purified returns to quench tower after heat exchange, to realize the recycle of quenched water; (3) catalyzer after separated and concentrated is carried out to drying treatment, reclaim catalyst particles; And (4) carry out cyclone deoiling to the washing water as stripping tower charging, to its purification and reclaim the sump oil that it is carried secretly, to realize the purify waste water object of water quality reaching standard of stripping tower, its concrete operation and effect are described below:
1. material properties and correlation parameter
In the reaction gas that contains a large amount of water vapour, be entrained with hydro carbons and enter quench tower together with catalyzer, the oleaginousness of reaction gas is about 2500mg/L, and catalyst content is about 400mg/L; The working temperature of quenched water is 109 ℃, and density is 915kg/m
3, catalyzer number average particle diameter is 1.19 microns, the water-filling density of catalyzer is 1400kg/m
3.At the bottom of quench tower, quenched water catalyst particles content is about 900mg/L.
2. the quenched water of methyl alcohol and carbon four alkene processed and the airtight coupling processing device of washing water
Be placed in respectively reaction gas cyclone purifier, the C4 reaction gas cyclone purifier at quench tower, C4 quench tower top, the reaction gas cyclone purifier of chilling tower top is equipped with 600 micro vortex flow tube groups, model is HL/G150-L less energy-consumption type micro vortex flow tube (East China University of Science's development), the C4 reaction gas cyclone purifier at C4 quench tower top is equipped with 100 micro vortex flow tube groups, and model is HL/G150-L less energy-consumption type micro vortex flow tube; The water wash column, the C4 water wash column that are connected with the top of quench tower, C4 quench tower respectively; The micro-cyclone clarificator and the micro-swirl concentrator that are connected in series with the bottom of quench tower, C4 quench tower, inner uniform 340 and 35 micro vortex flow tubes respectively of slight cyclone clarificator and thickener, wherein, micro vortex flow tube model is the development of HL/S25-L(East China University of Science) less energy-consumption type micro vortex flow tube; Be connected with the bottom of micro-swirl concentrator from returning charge blade dryer; And the washing water degreaser cyclone, the C4 washing water degreaser cyclone that are connected with the bottom of water wash column, C4 water wash column respectively, oil eliminator is built-in with micro vortex flow tube group, micro vortex flow tube group is comprised of 110 and 18 micro vortex flow tubes respectively, wherein, micro vortex flow tube model is HL/L28-L less energy-consumption type micro vortex flow tube (East China University of Science's development).
3. implementation process
As shown in Figure 1, after methyl alcohol and additive preheating, enter reactor reaction, it is cooling that the reaction gas generating and by product enter quench tower, and the reaction gas after the reaction gas cyclone purifier eddy flow of quench tower tower top purifies enters water wash column, and catalyst particles is separated arrival quench tower bottom; Reaction gas enters depropanizing tower after by compressor compresses after washing, and the following alkene of C4 enters subsequent processing and removes separation of olefins, and in order to improve product yield, C4 and above alkene return to C4 reactor and again carries out scission reaction; The washing water of water wash column bottom after the separation of washing water degreaser cyclone, oil recovery, washing water up to standard removes stripping tower;
Take reaction gas that C4 and above alkene obtains as raw material with take methyl alcohol as the reaction gas that raw material obtains the same, it is cooling that the reaction gas that C4 reactor generates and by product enter C4 quench tower, reaction gas after the C4 of quench tower tower top reaction gas cyclone purifier eddy flow purifies enters C4 water wash column, and catalyst particles is stayed C4 quench tower bottom; Reaction gas enters C4 depropanizing tower after by C4 compressor compresses after washing, and the following alkene of C4 enters subsequent processing and removes separation of olefins; The washing water of C4 water wash column bottom after the separation of C4 washing water degreaser cyclone, oil recovery, washing water up to standard removes stripping tower;
At the bottom of C4 quench tower tower, at the bottom of quenched water and MTO quench tower tower, quenched water passes through micro-cyclone clarificator and micro-swirl concentrator after converging successively, the quenched water of clarification after heat exchange as chilling agent return to MTO quench tower and C4 quench tower; The concentrated catalyst pulp obtaining through reclaiming catalyzer utilization after returning charge blade drier is dry;
The product of reactor bottom and air together enter revivifier regeneration, and the product of regeneration and air together enter the regeneration of C4 revivifier, the CO of generation, CO
2deng gas, by C4 revivifier top, discharged; The product circulation that regenerator bottoms is discharged enters reactor; The product circulation that C4 regenerator bottoms is discharged enters C4 reactor; The product of C4 reactor bottom and air together circulate and enter the regeneration of C4 revivifier.
4. interpretation of result
By using quenched water and the airtight coupling processing device of washing water of methyl alcohol and carbon four alkene processed, after reaction gas cyclone purifier eddy flow purifies, the oleaginousness of reaction gas is down to about 200mg/L by 2500mg/L, and catalyst content is down to about 50mg/L by 400mg/L; After liquid-solid separation and concentrating, the catalyst particles content of quenched water is down to 82mg/L by 915mg/L, and the rich catalyst pulp inner catalyst of underflow content reaches 45g/L; Liquid-solid separation accuracy is 1.0 μ m; The efficiency of described cyclone deoiling reaches 87%, and the oil-contg of stripping tower in purifying waste water is less than 10ppm.
In addition, by adopt quenched water and the airtight coupling processing technology of washing water in methyl alcohol and carbon four olefin process processed, make the reaction waste that produces in reaction process and quenched water, the whole hermetic reclaim utilizations of washing water, reaction used heat is utilized, the catalyzer reclaiming can be reused, and has reduced production cost, has extended device running period, also the volume of separating device has been reduced to approximately 10%, reduced manufacturing cost.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. the quenched water of methyl alcohol and carbon four alkene processed and the airtight coupled processing method of washing water, the method comprises the following steps:
(a) reaction gas of chilling tower top, C4 chilling tower top is carried out to eddy flow purification, catalyst particles and the liquid hydrocarbon to remove reaction gas, carried secretly; Reaction gas after purifying is washed, to realize the improvement of washing water water quality;
(b) quenched water containing catalyst particles at the bottom of quench tower, at the bottom of C4 quench tower is carried out to liquid-solid separation and concentrated, the quenched water after isolation of purified returns to quench tower after heat exchange, to realize the recycle of quenched water;
(c) catalyzer after separated and concentrated is carried out to drying treatment, reclaim catalyst particles; And
(d) washing water as stripping tower charging is carried out to cyclone deoiling, to its purification and reclaim the sump oil that it is carried secretly, to realize stripping tower the up to standard of water quality of purifying waste water.
2. the method for claim 1, is characterized in that, described in carry out the reaction gas of eddy flow purification oleaginousness be 1500-3000mg/L, catalyst content is 200-500mg/L.
3. method as claimed in claim 2, is characterized in that, after eddy flow purifies, the oleaginousness of reaction gas is down in 250mg/L, and catalyst content is down in 60mg/L.
4. the method for claim 1, is characterized in that, the working temperature of the described quenched water containing catalyst particles is 85-115 ℃, and density is 900-930kg/m
3, catalyst particle size is 1-20 micron, the water-filling density of catalyzer is 1200-1600kg/m
3.
5. the method for claim 1, is characterized in that, the catalyst particles content of the described quenched water containing catalyst particles is 600-1100mg/L.
6. method as claimed in claim 5, is characterized in that, liquid-solid separation and concentrated after, the catalyst particles content of quenched water is down in 100mg/L, the rich catalyst pulp inner catalyst of underflow content reach 40g/L or higher more than; Liquid-solid separation accuracy is 1 μ m.
7. the method for claim 1, is characterized in that, the efficiency of described cyclone deoiling reaches 85% or higher, and the oil-contg of stripping tower in purifying waste water is not more than 20ppm.
8. the quenched water of methyl alcohol and carbon four alkene processed and a washing water coupling processing device, this device comprises:
Be placed in respectively quench tower (4), the reaction gas cyclone purifier (5) at C4 quench tower (13) top, C4 reaction gas cyclone purifier (14), for the reaction gas of chilling tower top, C4 chilling tower top being carried out to eddy flow purification, catalyst particles and the liquid hydrocarbon carried secretly to remove reaction gas;
The water wash column (6), the C4 water wash column (15) that are connected with the top of quench tower (4), C4 quench tower (13) respectively, for the reaction gas after purifying is washed, to realize the improvement of washing water water quality;
The micro-cyclone clarificator (7-1) and the micro-swirl concentrator (7-2) that are connected in series with the bottom of quench tower (4), C4 quench tower (13), for the quenched water containing catalyst particles at the bottom of quench tower, at the bottom of C4 quench tower, carry out liquid-solid separation and concentrated, quenched water after isolation of purified returns to quench tower after heat exchange, to realize the recycle of quenched water;
Be connected with the bottom of micro-swirl concentrator (7-2) from returning charge blade dryer (8), for the catalyzer to after separated and concentrated, carry out drying treatment, reclaim catalyst particles; And
The washing water degreaser cyclone (8), the C4 washing water degreaser cyclone (16) that are connected with the bottom of water wash column (6), C4 water wash column (15) respectively, for the washing water as stripping tower charging is carried out to cyclone deoiling, to its purification and reclaim the sump oil that it is carried secretly, to realize stripping tower the up to standard of water quality of purifying waste water.
9. method as claimed in claim 8, it is characterized in that, described reaction gas cyclone purifier (5), C4 reaction gas cyclone purifier (14), micro-cyclone clarificator (7-1), micro-swirl concentrator (7-2), washing water degreaser cyclone (8) and C4 washing water degreaser cyclone (16) are composed in parallel by single or many eddy flow core pipes.
10. method as claimed in claim 8, it is characterized in that, the pressure-losses of described reaction gas cyclone purifier (5), C4 reaction gas cyclone purifier (14), micro-cyclone clarificator (7-1), micro-swirl concentrator (7-2), washing water degreaser cyclone (8) and C4 washing water degreaser cyclone (16) is 0.15-0.25MPa.
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CN105481166A (en) * | 2014-09-18 | 2016-04-13 | 山东龙港化工有限公司 | Quench water recovery treatment and recycling system of methanol-to-propylene device |
CN109205859A (en) * | 2018-11-14 | 2019-01-15 | 湖南泰山石环境科技有限公司 | A kind of methanol-to-olefins device generation water treatment system |
CN112827323A (en) * | 2021-01-20 | 2021-05-25 | 中国神华煤制油化工有限公司 | Purification system, purification method and application of methanol-to-olefin product gas |
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CN101352620A (en) * | 2008-09-09 | 2009-01-28 | 上海华畅环保设备发展有限公司 | Method and apparatus for micro hydrocyclone separation of MTO quench water and water of water-washing factory, and for concentration of fine catalyst in the same |
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CN103951098A (en) * | 2014-04-25 | 2014-07-30 | 江苏久吾高科技股份有限公司 | Solid and oil removal method and device for chilled water and washed water in MTO (methanol to olefin) process |
CN105481166A (en) * | 2014-09-18 | 2016-04-13 | 山东龙港化工有限公司 | Quench water recovery treatment and recycling system of methanol-to-propylene device |
CN109205859A (en) * | 2018-11-14 | 2019-01-15 | 湖南泰山石环境科技有限公司 | A kind of methanol-to-olefins device generation water treatment system |
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