CN101152994A - Method for refining carbonization crude benzole - Google Patents
Method for refining carbonization crude benzole Download PDFInfo
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- CN101152994A CN101152994A CNA2006101407167A CN200610140716A CN101152994A CN 101152994 A CN101152994 A CN 101152994A CN A2006101407167 A CNA2006101407167 A CN A2006101407167A CN 200610140716 A CN200610140716 A CN 200610140716A CN 101152994 A CN101152994 A CN 101152994A
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Abstract
The present invention relates to a refining method of coking crude benzol. The method has four sequential steps as follows: the pretreatment process of raw materials, the refining process of doffing non-arene and doffing othiophene, the deep desulfurization process of thiophene alkyl, and the refining process of toluene and xylene. The products of high-purity sulfur-free benzene, toluene and xylene can be made. The detailed technological process can be referred to the specification munual. Compared with the traditional pickling method, the present invention has the following advantages that: the whole process has no production of acid tar, no serious pollution to the environment and no serious corrosion of equipment; at the same time, the present invention avoids sulfonate loss of arene, effectively improves the reclamation rate of arene and belongs to an environmental friendly technology. Besides, the products of coking benzene category are obviously superior in quality to the traditional pickling. Compared with the catalytic hydrogenation process, the process is simple and not only can save a substantial amount of investment costs, but also the operation cost of device is low. The quality of benzene products is equivalent to hydrogenated benzene. The present invention provides an environmentally protective and economical process for the reasonable development and utilization of coking benzene resources, and has quite broad application prospects.
Description
Technical field
The present invention relates to chemical separation engineering and catalytic reaction engineering field, specifically, relate to a kind of environmentally friendly method for refining carbonization crude benzole, adopt extraction and distillation technology to remove impurity such as non-aromatics in the coking benzene, thiophene, and adopt the catalytic alkylation means that coking benzene is carried out deep desulfuration.
Background technology
Benzene, toluene are important basic Organic Chemicals, and one of its important source is the byproduct coking crude benzene of iron and steel enterprise and coking enterprise.Because crude benzol is formed complicated, contain many impurity, particularly thiophene and saturated alkane, when adopting traditional acid cleaning process that crude benzol is made with extra care, these impurity can not be removed fully, and then influence the quality of coking aromatic hydrocarbon product, particularly there are very big gap in the benzaldehyde product of many quality index of coking benzene and catalytic hydrofinishing and petroleum benzene, its range of application is very limited, therefore, sulfide and the saturated hydrocarbons impurity that removes in the coking benzene is the key that improves the benzene-type products quality, expands its Application Areas.
Method for refining carbonization crude benzole mainly contains catalytic hydrogenation process and sulfuric acid scrubbing technology at present.Generally adopt the shortening method for the large-tonnage coked crude benzene refining, this method adopts Co-Mo, Ni-W catalyst series, under high-temperature and high-pressure conditions, be that hydrogen sulfide is removed with the thiophene hydrocracking, unsaturated olefin is also saturated by hydrogenation simultaneously, separate saturated alkane impurity by extraction and distillation technology again, thereby obtain high-quality aromatic hydrocarbon product.Because this method reaction conditions is very harsh, sweetening process consumes hydrogen, complex technical process, so production cost is generally higher, simultaneously, thiophene is also decomposed generation hydrogen sulfide by hydrogenation and can't it be recycled, being not suitable for middle-size and small-size coal chemical enterprise applies, so domestic most of coal chemical enterprises still adopt traditional sulfuric acid scrubbing method technology at present.
Sulfuric acid scrubbing method technology comprises: 1. two benzene towers are cut into 150 ℃ of front-end volatiles (being the light benzene cut) and 150 ℃ of after cut (being heavy benzol) with crude benzol, and the benzene,toluene,xylene in the crude benzol more than 98% is transferred in the light benzene cut; 2. the light benzene cut is separated most of light constituent (as: dithiocarbonic anhydride, pentamethylene, normal hexane, cyclopentadiene etc.) wherein through primary tower from cat head, obtains mixed fraction at the bottom of the tower; 3. mixed fraction with enter pickling reactor after the vitriol oil about 95% mixes, reactions such as polymerization, sulfonation take place in impurity such as the unsaturated olefin in this moment this cut, thiophene under the effect of the vitriol oil; 4. add the water termination reaction after reacting certain hour, and mixture is introduced sour oily subsider isolate aromatic hydrocarbons, aromatic hydrocarbons enters the benzene blowing tower steaming and blows after alkali cleaning, to reclaim aromatic fraction, this cut obtains coking benzene, toluene and dimethylbenzene product more respectively after purified petroleum benzin tower, toluene tower, benzenol hydrorefining rectifying separation.The acid cleaning process process is simple, production cost is lower, technology is comparative maturity also, but the fatal defective of this technology is to produce a large amount of acid tar and sulfur waste acid when removing impurity such as thiophene and unsaturated hydrocarbons, environment is caused severe contamination, and this technology is to coking benzene, the purification degree of depth of toluene is not enough, wherein some and benzene, the approaching stable hydrocarbon of toluene relative volatility will enter into product as impurity, influence the purity of product, thiophene in the benzene can not thoroughly be removed simultaneously, these impurity are all with the follow-up production technique relevant with catalytic process of influence, as with the coking benzene being the synthetic cyclohexanone of raw material, the synthetic cis-butenedioic anhydride of coking benzene oxidation and nitrated system oil of mirbane and then hydrogenation production aniline process etc., so, also must carry out deep desulfuration to it.
The coking benzene deep desulfuration method has a lot, relatively be typically the thiophene impurities that adopts sorbent material to select trace in the absorption coking benzene, as adopt zeolite molecular sieves such as A, 13X, Y to be used for the coking benzene adsorption desulfurize through the metal ion exchanged modification, the loading capacity of the sorbent material of report is generally lower at present, regeneration period is short, and regenerative process often purges by elevated temperature heat nitrogen or the mode of oxygen-containing gas roasting, therefore, the technology of selection absorption thiophene deep purifying coking benzene does not still have the report of industrial applications so far.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and a kind of coked crude benzene refining technology is provided, adopt extracting rectifying isolation technique and catalytic alkylation means to substitute existing acid wash production technique, to produce high-purity sulfurless benzene.
The object of the invention can realize by following measure: the coking crude benzene of coking industry and/or iron and steel enterprise is undertaken by following four processing steps in sequence: raw materials pretreatment operation, non-aromatic removal hydrocarbon and take off thiophene refining step, thiophene alkylation deep desulfuration operation and toluene and dimethylbenzene refining step obtain the product of high-purity sulfurless benzene, toluene, dimethylbenzene.See Fig. 1.
(1) raw materials pretreatment operation:
The main purpose of this operation be for next step non-aromatic removal hydrocarbon with take off the thiophene refining step raw materials technology be provided, rectifying tower is main operating unit, promptly pass through distillation operation, the coking crude benzene cutting of iron and steel enterprise and/or coking enterprise production is obtained benzene front-end volatiles (containing the benzene cut) (or title benzene+benzene overhead distillate, together following) and toluene fraction, can take following A, B, three kinds of separation schemes of C to obtain above-mentioned two cuts, these two strands of cuts are directly as the raw material of extracting rectifying non-aromatic removal hydrocarbon.
Separation scheme A:
The raw material crude benzol through dehydration, filter, and be preheated to enter behind the bubble point temperature two benzene towers 1 separate light benzene cut (stream strand 1.) and heavy benzol; The light benzene cut separates toluene front-end volatiles (contain toluene fraction, promptly the stream thigh 2.) through Cutting Tap 2 with the toluene after cut; 2. the stream thigh separates with benzene front-end volatiles (containing the benzene cut) through benzene-toluene Cutting Tap 4 realization toluene fractions.Benzenol hydrorefining 3 is separated the dimethylbenzene cut in the toluene after cut.See Fig. 2.
Separation scheme B:
The raw material crude benzol through dehydration, filter, and be preheated to enter behind the bubble point temperature Cutting Tap 1 separate toluene front-end volatiles (contain toluene fraction, promptly stream strand 1.) and toluene after cut; 1. the stream thigh separates with benzene front-end volatiles (containing the benzene cut) through benzene-toluene Cutting Tap 3 realization toluene fractions.Benzenol hydrorefining 2 is separated the dimethylbenzene cut in the toluene after cut.See Fig. 3.
Separation scheme C:
The raw material crude benzol through dehydration, filter, and be preheated to enter behind the bubble point temperature benzene tower 1 separate benzene front-end volatiles (containing the benzene cut); Tower bottoms (promptly the stream thigh 1.) is separated toluene fraction and dimethylbenzene cut respectively through toluene tower 2 and benzenol hydrorefining 3.See Fig. 4.
(2) non-aromatic removal hydrocarbon and take off the thiophene refining step:
This operation is made up of non-aromatic removal hydrocarbon tower 1, benzene treating tower 2, solvent flashing jar 3, solvent regeneration tower 4, benzene recovery tower 5, solvent recovery tower 6 and toluene recovery tower 7.
Non-aromatic removal hydrocarbon tower will be from the benzene front-end volatiles (containing the benzene cut) of crude benzol pretreatment process and the most of non-aromatic impurity removal in the toluene fraction; especially remove dithiocarbonic anhydride wherein; cyclopentadiene impurity; selected extraction agent comprises dimethyl formamide; or glycols; or tetramethylene sulfone; or N-Methyl pyrrolidone; or N-formyl morpholine; or above-mentioned extraction agent blended double solvents by a certain percentage; (solvent ratio is meant the ratio of charging aromatic hydrocarbons and the mass velocity of extraction agent to solvent ratio; be generally 1: 1～12 down together); this tower is operated under normal pressure or reduced pressure, and the cat head service temperature is generally between 85 ℃～40 ℃.
Benzene front-end volatiles (containing the benzene cut) from the raw materials pretreatment operation, toluene fraction is respectively from tower 1 bottom and top different positions charging, from the cat head charging of the solvent of solvent flashing jar 3 from this tower, this tower working pressure is generally 0.2MPa～0.04MPa and (refers to absolute pressure, down together), overhead fraction is for comprising: unsaturated hydrocarbons is (as cyclopentadiene, methyl cyclopentadiene, cyclohexene etc.), stable hydrocarbon (normal hexane, cyclohexane, methyl cyclohexanol, 2-methyl-hexane, octane etc.), dithiocarbonic anhydride, impurity such as hydrogen sulfide, realize benzene by this tower, toluene and non-aromatics separate impurities, thereby the purity of raising benzene-type products.
The raw material of benzene treating tower comes from non-aromatic removal bottoms material and benzene recovery tower overhead benzene cut, extraction agent comes from the regenerated solvent of solvent regeneration tower, the material of tower 1 bottom (being rich solvent) with merge the middle part charging of back from benzene treating tower 2 from the overhead benzene cut of benzene recovery tower, solvent regeneration tower 4 through the regenerated solvents then from its top feed of tower 2, this tower working pressure is 0.2MPa～0.04MPa, corresponding cat head service temperature is generally between 95 ℃～45 ℃, solvent ratio is generally 1: 1～12, overhead fraction is for tentatively taking off the benzene cut behind the thiophene, and this cut will be as the raw material of thiophene alkylation deep desulfuration.
The purpose of solvent flashing jar is to realize separating of aromatic hydrocarbons and solvent, rich solvent from tower 2 bottom materials carries out adiabatic flash through flash tank 3 under the pressure about 0.025MPa～0.045MPa, solvent part after the flash distillation turns back to the cat head recycle of extractive distillation column 1, another part with enter solvent regeneration tower 4 in the lump from the solvent of solvent recovery tower 6 and regenerate, the working pressure of regenerator column is generally about 0.01MPa, clean solvent part after the regeneration turns back to benzin system Tata 2 tops, and another part turns back to benzene and reclaims Tata 5 tops.
Separate the benzene-thiophene-toluene fraction that obtains through flash tank 3 and after pump boosts, reclaim Tata 5 middle part chargings from benzene, this tower operational condition is identical with tower 2, the overhead benzene cut loops back benzene treating tower 2 as raw material, and tower bottom distillate separates solvent from the middle part charging of solvent recovery tower 6 with aromatic fraction.
Solvent recovery tower 6 is operated under 0.03MPa～0.06MPa pressure usually, between 75 ℃～45 ℃ of the corresponding tower top temperatures, enter benzene recovery Tata 5 tops at the bottom of the tower after a recovered solvent part and the regenerated solvent merging from solvent regeneration tower and recycle, another part then enters solvent regeneration tower 4 and regenerates; The aromatic fraction that cat head contains thiophene is delivered to toluene and is reclaimed Tata 7 and carry out rectifying separation.
Toluene reclaims Tata 7 and is mainly used in the benzene-toluene fraction that contain thiophene of separation from the solvent recuperation column overhead; the common atmospheric operation of this tower; the toluene fraction that obtains at the bottom of the tower enters the 4th operation, and to carry out toluene refining; the benzene of cat head-thiophene cut can be directly as the raw material of acetylization reaction Synthetic 2-acetyl thiophene; also can thiophene further be concentrated into more than 50% (weight), carry out acetylization reaction Synthetic 2-acetyl thiophene again by high-efficient spiral-screen column.Thiophene acetylize Synthetic 2-acetyl thiophene is referring to patent " a kind of is the method for raw material Synthetic 2-acetyl thiophene with the thiophene in the crude benzol ", and application number is 2003101152681.
More than Xu Shu process flow sheet is seen Fig. 5.
(3) thiophene alkylation deep desulfuration operation:
Thiophene alkylation deep desulfuration operation is made up of alkylation reactor and rectifying tower, and alkylation reactor adopts fixed-bed reactor usually.
Generally be not higher than 1000mg/L from thiophene concentration in the benzene cut of benzene treating tower 2 cats head of a last operation, in order to prepare the benzaldehyde product of total sulfur content less than 1ppm, further remaining thiophene impurities in the deep removal benzene cut also.For this reason, adopt solid acid catalyst catalysis thiophene and the alkylating method of unsaturated olefin, thiophene alkylation is converted into the higher relatively alkylthrophene of boiling point, by fractionation alkylthrophene is separated with benzene, and then reach the purpose of deep desulfuration.See Fig. 6.
The alkylating desulfurization unit comprises alkylation reactor 1, gas-liquid separator 2 and Cutting Tap 3 compositions, alkylation reactor adopts fixed bed usually, filling solid acid catalyst in the device, many Bronsted of containing acid site and (or) solid catalyst in Lewis acid site may be used to the alkylated reaction of catalysis thiophene and alkene, more typical Lewis acid comprises AlCl
3, FeCl
3, BF
3, ZnCl
2, SbCl
3, TiCl
4Deng, AlCl particularly
3, BF
3Load on the alkylated reaction that is used for thiophene on silicon-dioxide and the absorbent charcoal carrier and can embody high reaction activity and high.Typical B ronsted acid comprises H
2SO
4, HF, CHF
3O
3S (trifluoromethane sulfonic acid), polynite, atlapulgite, acidic zeolite, sulfonate resin etc., the acidic zeolite catalyzer comprises HZSM-5, HZSM-11, HZSM-12, HZSM-22, HZSM-35, H β, H-mordenite, HMCM-22, HMCM-41, HMCM-56, HY, H-USY and the prepared composite solid-acid catalyst of the above-mentioned zeolite-loaded Bronsted of containing acid and Lewis acid activity center.The unsaturated olefin that participates in alkylated reaction comprises ethene, propylene, butylene and isomer thereof, amylene and isomer thereof, all carbon numbers of alkene and isomer thereof are the monoene and the diolefine of the low-carbon alkene below 6.
Thiophene and alkene carry out alkylation reaction condition and is generally on solid acid catalyst: temperature of reaction is that room temperature～300 ℃, reaction pressure are that normal pressure～8.0MPa, coking benzene liquid feeding weight space velocity are 0.1～18h
-1, alkylating agent and thiophene mol ratio be in 1～1000 scope.
Generally, thiophene and ethylenic unsaturation alkylating hydrocarbons transformation efficiency all can be near 100% in the benzene, but carrying out along with reaction, activity of such catalysts can decrease, in order to guarantee that the benzaldehyde product total sulfur content is less than 1ppm, generally the adsorption desulfurize tower need be set after taking off the alkylthrophene rectifying tower, the unreacted thiophene of denier in the benzaldehyde product of rectifying tower side line extraction be removed by selecting absorption, to guarantee the benzaldehyde product quality.The sorbent material of adsorption tower filling normally passes through the zeolite molecular sieve of modification, comprises ZSM-5, ZSM-11, A, X, Y, USY, MCM-41 equimolecular sieve, and molecular sieve modified means generally adopt ion-exchange techniques, with Cu
2+, Ni
2+Be incorporated into zeolite framework.It is 0.1～100h that adsorption conditions is generally room temperature～150 ℃, normal pressure～5.0MPa, raw material weight air speed
-1
(4) toluene and dimethylbenzene refining step:
Toluene, dimethylbenzene refining step comprise clay-filtered tower, toluene tower, benzenol hydrorefining.Adopt clay-filtered tower at 120 ℃～300 ℃, normal pressure～8.0MPa, weight space velocity 0.1～100h respectively from the dimethylbenzene cut of operation (1) and the toluene fraction of operation (2)
-1Operate under the condition, the main purpose of this device is to remove impurity such as a spot of basic nitrogen compound, unsaturated hydrocarbons and vinylbenzene in toluene, the dimethylbenzene cut, so that meet the specification of quality of coking industry regulation through the product of toluene tower and benzenol hydrorefining rectifying gained.Toluene tower and benzenol hydrorefining are generally atmospheric operation, also can adopt decompression operation.
The present invention compares with existing production technology and has following advantage:
Compare with traditional acid wash technology, whole process can not produce acid tar, no longer to the environment structure severe contamination, can severe corrosion equipment yet, avoided the sulfonation loss of aromatic hydrocarbons simultaneously, effectively improve aromatic recovery rate, belong to environmentally friendly technology, and the coking benzene-type products quality of being produced obviously is better than traditional acid wash; Compare with catalytic hydrogenation process, this technical process is simple, not only can save a large amount of investment costs, and device running cost is cheap, the benzaldehyde product quality is suitable with hydrogenation benzene, this has found an environmental protection, economic operational path for rational exploitation and utilization coking benzene resource, has a very wide application prospect.
Description of drawings
Fig. 1 process flow sheet of the present invention
Fig. 2 raw material crude benzol separation scheme A schema
Fig. 3 raw material crude benzol separation scheme B schema
Fig. 4 raw material crude benzol separation scheme C schema
Fig. 5 non-aromatic removal hydrocarbon with take off thiophene refining step process flow sheet
1-non-aromatic removal hydrocarbon tower 2-benzene rectifying tower 3-solvent flashing jar 4-solvent regeneration tower 5-benzene reclaims
Tower 6-solvent recovery tower 7-toluene recovery tower
Fig. 6 thiophene alkylation deep desulfuration reaction member process flow sheet
1-thiophene alkylation reactor 2-gas-liquid separator 3-Cutting Tap
Embodiment
Below in conjunction with embodiment, in conjunction with the accompanying drawings, the present invention is further specified.But the present invention is not only limited to these embodiment:
Embodiment 1:
Coking crude benzene with coking enterprise production is raw material (wherein the mass content of benzene, toluene is respectively 68.8%, 12.1%), through dehydration, filtration solid impurity, and with its preheating, press crude benzol separation scheme A, middle part charging from two benzene towers 1, this tower normal pressure, semi continuous operation, crude benzol are split into and are lower than 150 ℃ of light benzene cuts (wherein thiophene concentration is 3350mg/L) and are higher than 150 ℃ of heavy benzol cuts; The light benzene cut distillates toluene front-end volatiles (containing toluene fraction) by Cutting Tap 2 again from cat head, tower bottom distillate obtains the dimethylbenzene cut through benzenol hydrorefining 3 rectifying separation.The toluene front-end volatiles that obtain from Cutting Tap 2 cats head are again through benzene-toluene Cutting Tap, realize separating of benzene front-end volatiles (containing the benzene cut) and toluene, and the benzene front-end volatiles of gained and toluene will be as the raw materials of non-aromatic removal hydrocarbon tower.
With after above-mentioned benzene front-end volatiles and the toluene fraction preheating respectively from the bottom and the top different positions charging of non-aromatic removal hydrocarbon tower, from the cat head charging of the N-Methyl pyrrolidone solvent of solvent flashing jar 3 from this tower, this tower atmospheric operation, between 57 ℃～60 ℃ of the cat head service temperatures, solvent ratio is 3, reflux ratio sets 25, overhead product is except containing the benzene about 15%, all the other are unsaturated hydrocarbons (as cyclopentadiene, methyl cyclopentadiene, cyclohexene etc.), stable hydrocarbon (normal hexane, cyclohexane, methyl cyclohexanol etc.), dithiocarbonic anhydride, impurity such as hydrogen sulfide, these impurity are sent into non-aromatic jar.The temperature of rich solvent is 120 ℃～125 ℃ at the bottom of the non-aromatic removal hydrocarbon tower, cool off through heat exchange, from benzene treating tower intermediate feed, cat head charging solvent is from the regenerated solvent of solvent regeneration tower, this tower atmospheric operation, corresponding cat head service temperature is 79.5 ℃～80.3 ℃, and the thiophene concentration in the overhead benzene cut is 210mg/L, and this cut will be as the raw material of the 3rd operation alkylation deep desulfuration; Tower bottom distillate enters the solvent flashing jar and carry out adiabatic flash under the pressure about 0.025MPa, solvent part after the flash distillation turns back to the cat head recycle of non-aromatic removal hydrocarbon tower 1, another part with enter solvent regeneration tower 4 in the lump from the hot solvent of solvent recovery tower 6 and regenerate, the working pressure of regenerator column is generally about 0.01MPa, clean solvent after the regeneration is through cooling, a part turns back to benzene treating tower 2 tops, and another part turns back to the top that benzene reclaims Tata 5.
Separate the benzene-thiophene-toluene fraction that obtains through flash tank 3 and after pump boosts and after the preheating, enter the benzene recovery tower, this tower operational condition is identical with tower 2, the benzene cut of recovered overhead is circulated to benzene treating tower 2, tower bottom distillate (being rich solvent) separates solvent from the middle part charging of solvent recovery tower 6 with aromatic fraction.Recovery tower 6 is operated under 0.045MPa pressure, and between 57 ℃～60 ℃ of the corresponding tower top temperatures, the aromatic fraction that cat head contains thiophene separates benzene-thiophene cut under normal pressure through toluene recovery tower 7 with toluene; A recovered solvent part enters solvent regeneration tower 4 and regenerates at the bottom of the tower, and another part then merges its top feed of back from thiophene upgrading tower 5 with clean solvent from regenerator column.
In order to obtain qualified toluene, dimethylbenzene product, need toluene fraction and dimethylbenzene cut are carried out carclazyte rectifying, purification condition is 180 ℃, 2.0MPa, weight space velocity 2h
-1, incite somebody to action wherein impurity such as a spot of basic nitrogen compound, unsaturated hydrocarbons, vinylbenzene, again through toluene tower and benzenol hydrorefining rectifying separation.Toluene tower and benzenol hydrorefining are generally atmospheric operation, also can adopt decompression operation.
Through behind the said process, total sulfur content 0.2ppm in the benzaldehyde product, the purity of benzene is greater than 99.9%, ctystallizing point is greater than 5.4 ℃, bromine index is 12.7mgBr/100g, toluene purity reaches 99% simultaneously, and toluene, dimethylbenzene quality product are not less than the first class index standard of GB/T2284-93 and GB/T2285-93 defined.
Embodiment 2:
Coking crude benzene with coking enterprise production is raw material (wherein the mass content of benzene, toluene is respectively 68.8%, 12.1%), through dehydration, filtration solid impurity, and with its preheating, press crude benzol separation scheme B, middle part charging from Cutting Tap 1, this tower normal pressure operate continuously, control tower still temperature is 126 ℃, and crude benzol is divided into toluene front-end volatiles (containing toluene fraction) and toluene after cut; Wherein the toluene front-end volatiles separate with toluene through benzene-toluene Cutting Tap realization benzene front-end volatiles (containing the benzene cut) again, and the toluene after cut is then separated dimethylbenzene through benzenol hydrorefining.
Choosing the N-formyl morpholine is solvent, and the solvent ratio of non-aromatic removal hydrocarbon tower is 3.5, and reflux ratio is 30, and other operational condition is with embodiment 1.At this moment, non-aromatic removal hydrocarbon column bottom temperature is controlled at 137 ℃～140 ℃, temperature is controlled at 190 ℃～193 ℃ at the bottom of the benzin system Tata, thiophene concentration in the benzin system column overhead benzene cut is 270mg/L, this cut carries out deep desulfuration to be handled through the thiophene alkylation unit, the catalyzer that is adopted is a sulfonate resin, temperature of reaction is 65 ℃, other condition is identical with embodiment 1, and the thiophene alkylation transformation efficiency is near 100%, and rectifying is taken off the operational condition of heavy constituent alkylthrophene still with embodiment 1, total sulfur content 0.2ppm in the resulting benzaldehyde product, benzene purity can reach 99.8%, and ctystallizing point is greater than 5.4 ℃, and bromine index is 15.6mgBr/100g.
Toluene, dimethylbenzene are made with extra care with embodiment 1, and the toluene purity after making with extra care is 99%, and toluene, dimethylbenzene quality product are not less than the first class index standard of GB/T2284-93 and GB/T2285-93 defined.
Embodiment 3:
Coking crude benzene with coking enterprise production is raw material (wherein the mass content of benzene, toluene is respectively 68.8%, 12.1%), through dehydration, filtration solid impurity, and with its preheating, press crude benzol separation scheme C, middle part charging from tower 1, this tower normal pressure operate continuously is divided into benzene front-end volatiles (containing the benzene cut) with crude benzol and distillates from cat head; Tower bottom distillate is separated toluene and dimethylbenzene cut through toluene tower 2 and benzenol hydrorefining 3.
Choosing tetramethylene sulfone is solvent, and the solvent ratio of non-aromatic removal hydrocarbon tower is 4.3, and working pressure 0.23MPa, column bottom temperature are controlled at 162 ℃～165 ℃, and the lean solvent feeding temperature is 105 ℃, and other operational condition is with embodiment 1.Benzin system column bottom temperature is controlled at 180 ℃～183 ℃, thiophene concentration in the benzin system column overhead benzene cut is 250mg/L, this cut carries out deep desulfuration to be handled through the thiophene alkylation unit, alkylating desulfurization adopts activated carbon supported 5% trifluoromethane sulfonic acid active ingredient as alkylation catalyst, propylene is an alkylating agent, in temperature of reaction is 75 ℃, normal pressure, the mol ratio of propylene and thiophene is 100, the comprehensive sample of reaction 200h is by rectifying tower rectifying excision heavy constituent alkylthrophene, the benzaldehyde product of side line extraction is after the CuY zeolite molecular sieve selects absorption further to take off thiophene (adsorption conditions is with embodiment 1), total sulfur content is lower than 0.5ppm in the benzene, ctystallizing point is greater than 5.4 ℃, and bromine index is 10.1mgBr/100g.
Toluene, dimethylbenzene refining step are with embodiment 1, and quality product meets the first class index standard of quality GB/T2284-93 and GB/T2285-93 defined.
Embodiment 4:
Coking crude benzene with coking enterprise production is raw material (wherein the mass content of benzene, toluene is respectively 68.8%, 12.1%), and the crude benzol pretreatment process is with embodiment 2, the non-aromatic removal hydrocarbon with take off the thiophene refining step with embodiment 1.
The catalyzer that the benzene cut alkylation deep desulfuration of benzene treating tower is adopted is the H beta-molecular sieve, isopentene is an alkylating agent, be under 50 the reaction conditions in the mol ratio of 200 ℃, 2.0MPa, isopentene and thiophene, the comprehensive sample of reaction 500h is by rectifying tower rectifying excision heavy constituent alkylthrophene, and the benzaldehyde product of side line extraction is through Cu
2+The Y molecular sieve of ion-exchanged is selected absorption back (adsorption conditions is with embodiment 1), and benzene thiophene content is lower than 0.1mg/L, and ctystallizing point is greater than 5.4 ℃, and bromine index is 5.1mgBr/100g.
Embodiment 5:
Coking crude benzene with coking enterprise production is raw material (wherein the mass content of benzene, toluene is respectively 68.8%, 12.1%), the crude benzol pretreatment process is with embodiment 2, the non-aromatic removal hydrocarbon with take off the thiophene refining step with embodiment 2, and non-aromatic removal hydrocarbon tower and benzene treating tower theoretical plate number are improved 20%.Thiophene concentration can reach 97mg/L in the benzene cut of benzene treating tower, and this cut carries out the alkylation deep desulfuration, and the catalyzer that is adopted changes the H through 0.5mol/L into
2SO
4The USY zeolite molecular sieve of dipping modification, iso-butylene is an alkylating agent, be that the comprehensive sample of reaction 1000h is by rectifying tower rectifying excision heavy constituent alkylthrophene under 60 the reaction conditions in the mol ratio of 80 ℃, normal pressure, iso-butylene and thiophene, the benzaldehyde product of side line extraction is through Cu
2+The Y molecular sieve of ion-exchanged is selected absorption back (adsorption conditions is with embodiment 1), and at this moment, benzaldehyde product purity can reach 99.96%, and benzene thiophene content is lower than 0.1mg/L, and ctystallizing point is greater than 5.4 ℃, and bromine index is 6.1mgBr/100g.
Claims (5)
1. method for refining carbonization crude benzole, it is characterized in that: the coking crude benzene of coking industry and/or iron and steel enterprise is undertaken by following four processing steps in sequence: raw materials pretreatment operation, non-aromatic removal hydrocarbon and take off thiophene refining step, thiophene alkylation deep desulfuration operation and toluene and dimethylbenzene refining step obtain the product of high-purity sulfurless benzene, toluene, dimethylbenzene.
2. method for refining carbonization crude benzole according to claim 1, it is characterized in that: the raw materials pretreatment operation, pass through distillation operation, coking crude benzene is taked A, B, three kinds of separation schemes of C, cutting obtains benzene front-end volatiles and toluene fraction, and these two strands of cuts are directly as the raw material of extracting rectifying non-aromatic removal hydrocarbon;
Separation scheme A:
The raw material crude benzol through dehydration, filter, and be preheated to enter behind the bubble point temperature two benzene towers separate light benzene cut and heavy benzol; The light benzene cut separates the toluene front-end volatiles through Cutting Tap with the toluene after cut; The toluene front-end volatiles separate with the benzene front-end volatiles through benzene-toluene Cutting Tap realization toluene fraction; Benzenol hydrorefining is separated the dimethylbenzene cut in the toluene after cut;
Separation scheme B:
The raw material crude benzol through dehydration, filter, and be preheated to enter behind the bubble point temperature Cutting Tap separate toluene front-end volatiles and toluene after cut; The toluene front-end volatiles separate with the benzene front-end volatiles through benzene-toluene Cutting Tap realization toluene fraction; Benzenol hydrorefining is separated the dimethylbenzene cut in the toluene after cut;
Separation scheme C:
The raw material crude benzol through dehydration, filter, and be preheated to enter behind the bubble point temperature benzene tower separate the benzene front-end volatiles; Tower bottoms is separated toluene fraction and dimethylbenzene cut respectively through toluene tower and benzenol hydrorefining.
3. method for refining carbonization crude benzole according to claim 1 is characterized in that this operation non-aromatic removal hydrocarbon and takes off the thiophene refining step being made up of non-aromatic removal hydrocarbon tower, benzene treating tower, solvent flashing jar, solvent regeneration tower, benzene recovery tower, solvent recovery tower, toluene recovery tower;
Non-aromatic removal hydrocarbon tower will be from the benzene front-end volatiles (containing the benzene cut) of crude benzol pretreatment process and the most of non-aromatic impurity removal in the toluene fraction, especially remove wherein dithiocarbonic anhydride, cyclopentadiene impurity, selected extraction agent comprises dimethyl formamide or glycols or tetramethylene sulfone or N-Methyl pyrrolidone or N-formyl morpholine or above-mentioned extraction agent blended double solvents by a certain percentage, solvent ratio is generally 1: 1-12, this tower is at normal pressure or decompression operation, and the cat head service temperature is generally between 85 ℃～40 ℃;
The raw material of benzene treating tower comes from non-aromatic removal hydrocarbon Tata substrate material and benzene recovery tower overhead benzene cut, extraction agent comes from the regenerated solvent of solvent regeneration tower, this tower is operated under 0.2MPa～0.04MPa pressure, the cat head service temperature is between 100 ℃～45 ℃, solvent ratio is generally 1: 1～12, realizes the initial gross separation of benzene and thiophene by this tower;
The rich solvent that the solvent flashing jar will come from the bottom of the benzin system Tata carries out flash distillation, solvent part after the flash distillation is got back to the non-aromatic removal column overhead, and another part then treats that with the part that comes from solvent recovery tower the merging of regenerated solvent enters solvent regeneration tower and carries out solvent reclamation;
Solvent regeneration tower is generally negative-pressure operation, and the solvent part after the regeneration enters benzin system column overhead, and another part then enters benzene recovery tower cat head;
The raw material of benzene recovery tower comes from solvent flashing jar tank deck and separates the benzene-thiophene-toluene fraction that obtains, this tower operational condition is with the benzene treating tower, be circulated to the further refining and recovery benzene of benzene treating tower from cat head distilled benzene cut, rich solvent reclaims solvent through solvent recovery tower at the bottom of the tower;
Solvent recovery tower is operated under normal pressure or reduced pressure, 84 ℃～40 ℃ of corresponding cat head service temperatures, enter benzene recovery tower cat head after a recovered solvent part and the regenerated solvent merging from solvent regeneration tower at the bottom of the tower and recycle, another part then enters solvent regeneration tower and regenerates;
Overhead fraction then separates benzene-thiophene through the toluene recovery tower with toluene fraction.
4. method for refining carbonization crude benzole according to claim 1 is characterized in that thiophene alkylation deep desulfuration operation is made up of alkylation reactor and rectifying tower; Alkylation reactor adopts fixed-bed reactor usually, filling solid acid catalyst in the reactor, and energy catalysis thiophene and insatiable hunger are that the catalyzer of olefin alkylation comprises Lewis acid, as AlCl
3, FeCl
3, BF
3, ZnCl
2, SbCl
3, TiCl
4Also comprise Bronsted acid, as H
2SO
4, HF, trifluoromethane sulfonic acid CHF
3O
3S, polynite, atlapulgite, acidic zeolite, sulfonate resin, acidic zeolite catalyzer comprise HZSM-5, HZSM-11, HZSM-12, HZSM-22, HZSM-35, H β, H-mordenite, HMCM-22, HMCM-41, HMCM-56, HY, H-USY and the prepared composite solid-acid catalyst of the above-mentioned zeolite-loaded Bronsted of containing acid and Lewis acid activity center; The unsaturated olefin that participates in alkylated reaction comprises that all carbon numbers of ethene, propylene, butylene and isomer thereof, amylene and isomer thereof, hexene and isomer thereof are the monoene and the diolefine of the low-carbon alkene below 6; Thiophene and alkene carry out alkylation reaction condition and is generally on solid acid catalyst: temperature of reaction is that room temperature～300 ℃, reaction pressure are that normal pressure～8.0MPa, coking benzene liquid feeding weight space velocity are 0.1～18h
-1, alkylating agent and thiophene mol ratio be in 1～1000 scope.
5. method for refining carbonization crude benzole according to claim 1 is characterized in that toluene, dimethylbenzene refining step comprise white treating tower, toluene tower, the benzenol hydrorefining gone up; Clay-filtered tower is at 120 ℃～300 ℃, normal pressure～8.0MPa, weight space velocity 0.1～100h
-1Operate under the condition, the main purpose of this device is to remove impurity such as a spot of basic nitrogen compound, unsaturated hydrocarbons, vinylbenzene in toluene, the dimethylbenzene cut, so that meet the specification of quality of coking industry regulation through the product of toluene tower and benzenol hydrorefining rectifying gained; Toluene tower and benzenol hydrorefining are generally atmospheric operation, also can adopt decompression operation.
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|---|---|---|---|
| CNA2006101407167A CN101152994A (en) | 2006-09-30 | 2006-09-30 | Method for refining carbonization crude benzole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724427A (en) * | 2009-12-24 | 2010-06-09 | 中国寰球工程公司 | Rectification system for separating mixture rich in aromatic hydrocarbon |
| CN102617265A (en) * | 2011-01-30 | 2012-08-01 | 江苏永鹏科技实业有限公司 | Refined crude benzene and method for extracting thiophene |
| CN101514136B (en) * | 2009-03-31 | 2013-03-20 | 山东元利科技股份有限公司 | Method for preparing high purity toluene from coking crude benzene |
| CN105732292A (en) * | 2016-03-31 | 2016-07-06 | 中山大学 | Sulfolane aromatic hydrocarbon extraction distillation device with half-lean solution cycle logistics |
| CN106008139A (en) * | 2016-05-23 | 2016-10-12 | 临涣焦化股份有限公司 | Coking crude benzolhydrogenation recovery device |
| CN106916044A (en) * | 2015-12-24 | 2017-07-04 | 上海宝钢化工有限公司 | A kind of method for refining carbonization crude benzole |
| CN108002974A (en) * | 2017-12-15 | 2018-05-08 | 武汉钢铁有限公司 | The process of refined coking crude benzene |
| CN115155460A (en) * | 2022-07-11 | 2022-10-11 | 福建永荣科技有限公司 | Benzene desulfurization adsorber for alkene method cyclohexanol process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514136B (en) * | 2009-03-31 | 2013-03-20 | 山东元利科技股份有限公司 | Method for preparing high purity toluene from coking crude benzene |
| CN101724427A (en) * | 2009-12-24 | 2010-06-09 | 中国寰球工程公司 | Rectification system for separating mixture rich in aromatic hydrocarbon |
| CN101724427B (en) * | 2009-12-24 | 2013-02-13 | 中国寰球工程公司 | Rectification system for separating mixture rich in aromatic hydrocarbon |
| CN102617265A (en) * | 2011-01-30 | 2012-08-01 | 江苏永鹏科技实业有限公司 | Refined crude benzene and method for extracting thiophene |
| CN106916044A (en) * | 2015-12-24 | 2017-07-04 | 上海宝钢化工有限公司 | A kind of method for refining carbonization crude benzole |
| CN105732292A (en) * | 2016-03-31 | 2016-07-06 | 中山大学 | Sulfolane aromatic hydrocarbon extraction distillation device with half-lean solution cycle logistics |
| CN105732292B (en) * | 2016-03-31 | 2018-04-06 | 中山大学 | A kind of sulfolane aromatic hydrocarbons extraction distilling apparatus with semi lean solution circulation logistics |
| CN106008139A (en) * | 2016-05-23 | 2016-10-12 | 临涣焦化股份有限公司 | Coking crude benzolhydrogenation recovery device |
| CN106008139B (en) * | 2016-05-23 | 2019-04-02 | 临涣焦化股份有限公司 | A kind of coking crude benzene adds hydrogen recovery unit |
| CN108002974A (en) * | 2017-12-15 | 2018-05-08 | 武汉钢铁有限公司 | The process of refined coking crude benzene |
| CN115155460A (en) * | 2022-07-11 | 2022-10-11 | 福建永荣科技有限公司 | Benzene desulfurization adsorber for alkene method cyclohexanol process |
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