Background technology
Crude benzol is to reclaim a kind of benzoline that obtains from the pyrogenic raw gas of coal, main component is that middle benzene,toluene,xylene content accounts for more than 90%, because the technology of sulfuric acid washing method processing exists product yield low, the acid tar serious environment pollution of by-product and being eliminated generally all adopts the shortening method to handle crude benzol at present.
The sixties in 20th century, U.S. Hu Deli air products company succeeds in developing high temperature crude benzole hydrogenation process for refining (Litol method) system purified petroleum benzin, this technology at high temperature (600~630 ℃), high pressure (under 5.7~6.0MPa) by hydrofining and dealkylation, producing purity is 99.9%, the purified petroleum benzin product of S<1.5ppm.
The eighties in 20th century, the U.S. and Germany succeed in developing low temperature hydrogenation purification techniques in the crude benzol (tetramethylene sulfone and KK method) again in succession, this technology at middle low temperature (320~380 ℃), middle pressure (under 3.5~3.7MPa) by hydrofining and extractive distillation, produce the benzene,toluene,xylene product, product purity 〉=99.9%, S<0.5ppm, yield is about 98%.
More than three kinds of crude benzole hydrogenation technology more complicated, hydrogenation reaction is secondary, is divided into pre-reaction and main reaction, as not carrying out pre-reaction, main reactor is prone to coking so, phenomenons such as obstruction can not normally be carried out reaction.
Chinese patent CN 101028985A (application number 200610136857.1), a kind of method by preparing benzene aromatic hydrocarbon by crude benzene is disclosed, the situation that polymerization, coking etc. influence the reactor operation takes place in order to solve in it when Unstable Substances such as a small amount of diolefine, vinylbenzene, indenes, indane, colloid heat in the crude benzol, the atmosphere 3rd side cut oil (straight-run diesel oil) that in crude benzol, adds 1: 9~9: 1, thereby cancellation prefractionation and pre-hydrogenation, hydrogenated oil enters to take off sends into extraction process after heavies column removes heavy constituent.This characteristic feature of an invention is to add a large amount of atmosphere 3rd side cut oil to dilute Unstable Substance in the raw material in the crude benzol raw material, thereby prevents the coking of hydrogenation reaction, latch up phenomenon; Shortcoming is the energy consumption that has increased production process, has increased the regeneration scheme device of atmosphere 3rd side cut oil, and oil still needs through removing heavy constituent behind the hydrogenation, and is consistent with traditional fore-distillation function.
Chinese patent CN 1948244A (application number 200610022254.9), a kind of technology by coking benzene hydrogenation desulfurization denitrogenation producing refined benzene is disclosed, this working method is pre-treatment and three grades of production technique that hydrogenation combines, pre-treatment obtains the benzene,toluene,xylene cut and enters hydrogenation reaction for removing heavy constituent.Hydrogenation reaction is three grades, and one-level is by the preliminary hydrogenating desulfurization of NiMo catalyzer, and secondary is by the denitrogenation of CoMoXP catalyst desulfurizing, and three grades remove inorganic sulfur by ZnO.The characteristics of this technology be the purified petroleum benzin content that obtains greater than 99.9%, sulphur content is less than 1mg/l, nitrogen content is less than 5mg/l; Shortcoming is a complex technical process, and investment, process cost is big.
Summary of the invention
The technology that the objective of the invention is a kind of preparing benzene aromatic hydrocarbon by crude benzene of designing at the deficiencies in the prior art, its adopts single-stage hydrogenation reaction, and low pressure is produced highly purified aromatic hydrocarbon product, and technology is simple, and is easy to operate, and constant product quality, and energy consumption is low.
The object of the present invention is achieved like this: a kind of technology of preparing benzene aromatic hydrocarbon by crude benzene, characteristics are that the crude benzol raw material filters after fore-distillation, and cat head is isolated the light constituent that comprises benzene, toluene, and side line extraction dimethylbenzene and vinylbenzene separate heavy benzol at the bottom of the tower; The cat head light constituent mixes the evaporation back with hydrogen and carry out hydrogenation reaction in the single-stage reactor of hydrogenation catalyst is housed in evaporator tower, simultaneously the saturated diolefine of hydrogenation, alkene; After the hydrogenated oil desulfurization that hydrogenation reaction obtains, the denitrogenation, obtain the grade oil benzene aromatic hydrocarbon through extraction and rectifying, concrete technology may further comprise the steps:
(1) fore-distillation
The crude benzol raw material heats up in a steamer in advance through being admitted to distillation tower behind the filtration of filter, well heater and heat exchange to 50~100 ℃, the working pressure of tower is 40KPa, temperature is 50~150 ℃, cat head extraction BT light benzene cut advances return tank, part is made trim the top of column liquid, part is then gone the hydrogenation operation, and the trim the top of column ratio is 0.6; Tower middle part side line extraction dimethylbenzene and small amount of toluene, vinylbenzene cut send benzenol hydrorefining rectifying; Extraction heavy benzol at the bottom of the tower send heavy constituent product storage tank.
(2) hydrogenation
The BT light benzene cut of sending here from the fore-distillation operation advances evaporator tower and hydrogen and evaporates laggard process furnace with 1: 500~1000 volume ratio thorough mixing, is heated to 250~350 ℃ and send hydrogenator; After then heating, evaporator tower bottom overhead product returns distillation tower; Material is sent into medial launder after the hydrogenation reaction, and gas phase is through knockout drum, and the hydrogen after the separation returns evaporator tower hydrogenation usefulness, and liquid phase is gone the stripping operation after then flowing into medial launder.
(3) stripping
The material that hydrogenation operation medial launder is sent here advances the stabilizer tower stripping, and the tower working pressure is 555~580KPa, and temperature is 120~162 ℃, light constituent H
2By stripping, benzene and toluene fraction then remove extraction process to S after the interchanger cooling at the bottom of tower from cat head.
(4) extraction
Send here through cooled benzene and toluene fraction middle part from the stripping operation and to add from distillation tower, solvent then adds from tower top, the tower working pressure is 90~150KPa, temperature is 130~165 ℃, the non-aromatics gas of top of tower extraction cools off laggard separating tank through interchanger, phlegma is through gas-liquid separation rear section reflux column, and part is then removed non-aromatics product storage tank, and reflux ratio is 0.6~0.9; The bottomsstream recovery process that desolvates.
(5) solvent recuperation
The bottomsstream that extraction process is sent here enters the recovery tower distillation, the tower working pressure is 50KPa, temperature is 130~176 ℃, the aromatic hydrocarbons gas and the steam of cat head cool off laggard separating tank through interchanger, phlegma returns cat head through the gas-liquid separation rear section as phegma, it is 0.736 that part is then removed rectification working process, reflux ratio; The bottomsstream partly advances regenerator column purifies, and part is then returned distillation tower and made solvent usefulness, and its splitting ratio is 0.1~0.2, and the tower working pressure is 80~90KPa, and temperature is 175~180 ℃.
(6) rectifying of purified petroleum benzin, toluene
The aromatic hydrocarbons that the solvent recuperation operation is sent here adds from benzene tower middle part, the tower working pressure is 70~110KPa, service temperature is 98~141 ℃, the cat head gas phase is cooled off laggard storage tank through interchanger, the phlegma part enters the benzene tower as phegma, and part is then returned the distillation tower extraction, and reflux ratio is 2.09, tower top extraction purified petroleum benzin product, extraction toluene product at the bottom of the tower.
(7) rectifying of dimethylbenzene
The cut of distillation Tata medial side line extraction is entered benzenol hydrorefining, the tower working pressure is 70KPa, temperature is 90~104 ℃, the cat head gas phase is cooled off laggard storage tank through interchanger, phlegma is partly delivered to the crude benzol raw material tank, and all the other backflow benzenol hydrorefinings are made trim the top of column liquid, and reflux ratio is 100, tower top side line extraction dimethylbenzene product, tower bottom extraction reorganization dispensed product storage tank.
Described hydrogenation reaction adopts cobalt-molybdenum catalyst, and hydrogen pressure is 2.5~3.0MPa, and the liquid air speed is 0.5~3.0h
-1
Described extraction solvent is a tetramethylene sulfone.
It is simple that the present invention compared with prior art has technology, easy to operate, the aromatic hydrocarbon product purity height that low pressure is produced, steady quality, energy consumption is low, and the equipment of whole production device reduces, invest low, and the corrosion to equipment also reduces greatly in the production process, has improved the cycle of operation of equipment, and economic benefit is very remarkable.
Embodiment
Consult accompanying drawing 1, the present invention is undertaken by following processing step:
Embodiment 1
One, fore-distillation
The crude benzol raw material filter through filter 11, well heater 12 and heat exchange to 70 ℃ after be admitted to distillation tower 1 and heat up in a steamer in advance, the tower working pressure is 40KPa, temperature is 110 ℃, cat head extraction BT light benzene cut advances return tank 13, part is made trim the top of column liquid, and part is then gone the hydrogenation operation, and the trim the top of column ratio is 0.6; Tower middle part side line extraction dimethylbenzene and small amount of toluene, vinylbenzene cut send benzenol hydrorefining 10 rectifying; Extraction heavy benzol at the bottom of the tower send heavy constituent product storage tank.
Two, hydrogenation
The BT light benzene cut of sending here from the fore-distillation operation advances evaporator tower 2 and hydrogen and evaporates laggard process furnace 3 with 1: 650 volume ratio thorough mixing, be heated to 300 ℃ and send hydrogenator 4, hydrogenation reaction adopts cobalt-molybdenum catalyst, the condition of reaction control is: 298 ℃ of temperature, the hydrogen of evaporator tower 2 is carried by hydrogen make-up press 14, its pressure is 2.50MPa, liquid air speed 0.75h
-1Return distillation tower 1 after 12 heating of evaporator tower 2 bottom overhead product heater vias; Material is sent into medial launder 16 after the hydrogenation reaction, and the hydrogen of gas phase after knockout drum 17 separates returns evaporator tower 2 circulation hydrogenation by recycle hydrogen press 15 and uses, and liquid phase is removed stabilizer tower 5 strippings after then flowing into medial launder 16.
Three, stripping
The material that hydrogenation operation medial launder 16 is sent here advances stabilizer tower 5 strippings, and the tower working pressure is 570KPa, and temperature is 136 ℃, by steam stripped harmful light constituent H
2S discharges off gas treatment from cat head, and benzene and toluene fraction then remove extraction process after interchanger 18 coolings at the bottom of tower.
Four, extraction
Send here through cooled benzene and toluene fraction from the stripping operation and to add from distillation tower 6 middle parts, the extraction solvent tetramethylene sulfone then adds from tower top, and distillation tower 6 adopts the tetramethylene sulfone extractive distillations, and the working pressure of extractive distillation is 95KPa, and temperature is 145 ℃.The non-aromatics gas of top of tower extraction is through the laggard separating tank 20 of interchanger 19 coolings, and phlegma is through gas-liquid separation rear section reflux column 6, and part is then removed non-aromatics product storage tank, and reflux ratio is 0.65; The bottomsstream recovery process that desolvates.
Five, solvent recuperation
The bottomsstream that extraction process is sent here enters recovery tower 7 distillations, the tower working pressure is 50KPa, temperature is 167 ℃, the aromatic hydrocarbons gas of cat head and steam are through the laggard separating tank 22 of interchanger 21 coolings, phlegma returns cat head through the gas-liquid separation rear section as phegma, it is 0.736 that part is then removed rectification working process, reflux ratio; The bottomsstream partly advances regenerator column 8 purifies, and part is then returned distillation tower 6 and made solvent usefulness, and its splitting ratio is 0.12, and the tower working pressure is 85KPa, and temperature is 176 ℃.
Six, the rectifying of purified petroleum benzin, toluene
The aromatic hydrocarbons that the solvent recuperation operation is sent here adds from benzene tower 9 middle parts, the tower working pressure is 100KPa, service temperature is 140 ℃, the cat head gas phase is through the laggard storage tank 24 of interchanger 23 coolings, the phlegma part enters benzene tower 9 as phegma, and part is then returned distillation tower 6 extractions, and reflux ratio is 2.09, tower top extraction purified petroleum benzin product, extraction toluene product at the bottom of the tower.
Seven, the rectifying of dimethylbenzene
The cut of distillation tower 1 tower middle part side line extraction is entered benzenol hydrorefining 10, the tower working pressure is 70KPa, temperature is 104 ℃, the cat head gas phase is through the laggard storage tank 26 of interchanger 25 coolings, phlegma is partly delivered to the crude benzol raw material tank, and all the other backflow benzenol hydrorefinings 10 are made trim the top of column liquid, and its reflux ratio is 100, Tata top side line extraction dimethylbenzene product, bottom extraction reorganization dispensed product storage tank.
The quality such as the following table of the character of hydrogenating materials oil, hydrogenated oil, composition and extraction back product:
Embodiment 2
One, fore-distillation
The crude benzol raw material filter through filter 11, well heater 12 and heat exchange to 80 ℃ after be admitted to distillation tower 1 and heat up in a steamer in advance, the tower working pressure is 40KPa, temperature is 125 ℃, cat head extraction BT light benzene cut advances return tank 13, part is made trim the top of column liquid, and part is then gone the hydrogenation operation, and the trim the top of column ratio is 0.6; Tower middle part side line extraction dimethylbenzene and small amount of toluene, vinylbenzene cut send benzenol hydrorefining 10 rectifying; Extraction heavy benzol at the bottom of the tower send heavy constituent product storage tank.
Two, hydrogenation
The BT light benzene cut of sending here from the fore-distillation operation advances evaporator tower 2 and hydrogen and evaporates laggard process furnace 3 with 1: 800 volume ratio thorough mixing, be heated to 320 ℃ and send hydrogenator 4, hydrogenation reaction adopts cobalt-molybdenum catalyst, the condition of reaction control is: 305 ℃ of temperature, the hydrogen of evaporator tower 2 is carried by hydrogen make-up press 14, its pressure is 3.0MPa, liquid air speed 1.25h
-1Return distillation tower 1 after 12 heating of evaporator tower 2 bottom overhead product heater vias; Material is sent into medial launder 16 after the hydrogenation reaction, and the hydrogen of gas phase after knockout drum 17 separates returns evaporator tower 2 circulation hydrogenation by recycle hydrogen press 15 and uses, and liquid phase is removed stabilizer tower 5 strippings after then flowing into medial launder 16.
Three, stripping
The material that hydrogenation operation medial launder 16 is sent here advances stabilizer tower 5 strippings, and the tower working pressure is 580KPa, and temperature is 150 ℃, by steam stripped harmful light constituent H
2S discharges off gas treatment from cat head, and benzene and toluene fraction then remove extraction process after interchanger 18 coolings at the bottom of tower.
Four, extraction
Send here through cooled benzene and toluene fraction from the stripping operation and to add from distillation tower 6 middle parts, the extraction solvent tetramethylene sulfone then adds from tower top, and distillation tower 6 adopts the tetramethylene sulfone extractive distillations, and the working pressure of extractive distillation is 125KPa, and temperature is 158 ℃.The non-aromatics gas of top of tower extraction is through the laggard separating tank 20 of interchanger 19 coolings, and phlegma is through gas-liquid separation rear section reflux column 6, and part is then removed non-aromatics product storage tank, and reflux ratio is 0.75; The bottomsstream recovery process that desolvates.
Five, solvent recuperation
The bottomsstream that extraction process is sent here enters recovery tower 7 distillations, the tower working pressure is 50KPa, temperature is 150 ℃, the aromatic hydrocarbons gas of cat head and steam are through the laggard separating tank 22 of interchanger 21 coolings, phlegma returns cat head through the gas-liquid separation rear section as phegma, it is 0.736 that part is then removed rectification working process, reflux ratio; The bottomsstream partly advances regenerator column 8 purifies, and part is then returned distillation tower 6 and made solvent usefulness, and its splitting ratio is 0.15, and the tower working pressure is 88KPa, and temperature is 178 ℃.
Six, the rectifying of purified petroleum benzin, toluene
The aromatic hydrocarbons that the solvent recuperation operation is sent here adds from benzene tower 9 middle parts, the tower working pressure is 90KPa, service temperature is 120 ℃, the cat head gas phase is through the laggard storage tank 24 of interchanger 23 coolings, the phlegma part enters benzene tower 9 as phegma, and part is then returned distillation tower 6 extractions, and reflux ratio is 2.09, tower top extraction purified petroleum benzin product, extraction toluene product at the bottom of the tower.
Seven, the rectifying of dimethylbenzene
The cut of distillation tower 1 tower middle part side line extraction is entered benzenol hydrorefining 10, the tower working pressure is 70KPa, temperature is 95 ℃, the cat head gas phase is through the laggard storage tank 26 of interchanger 25 coolings, phlegma is partly delivered to the crude benzol raw material tank, and all the other backflow benzenol hydrorefinings 10 are made trim the top of column liquid, and its reflux ratio is 100, Tata top side line extraction dimethylbenzene product, bottom extraction reorganization dispensed product storage tank.
The quality such as the following table of the character of hydrogenating materials oil, hydrogenated oil, composition and extraction back product:
Embodiment 3
One, fore-distillation
The crude benzol raw material filter through filter 11, well heater 12 and heat exchange to 95 ℃ after be admitted to distillation tower 1 and heat up in a steamer in advance, the tower working pressure is 40KPa, temperature is 150 ℃, cat head extraction BT light benzene cut advances return tank 13, part is made trim the top of column liquid, and part is then gone the hydrogenation operation, and the trim the top of column ratio is 0.6; Tower middle part side line extraction dimethylbenzene and small amount of toluene, vinylbenzene cut send benzenol hydrorefining 10 rectifying; Extraction heavy benzol at the bottom of the tower send heavy constituent product storage tank.
Two, hydrogenation
The BT light benzene cut of sending here from the fore-distillation operation advances evaporator tower 2 and hydrogen and evaporates laggard process furnace 3 with 1: 950 volume ratio thorough mixing, be heated to 345 ℃ and send hydrogenator 4, hydrogenation reaction adopts cobalt-molybdenum catalyst, the condition of reaction control is: 310 ℃ of temperature, the hydrogen of evaporator tower 2 is carried by hydrogen make-up press 14, its pressure is 2.8MPa, liquid air speed 2.5h
-1Return distillation tower 1 after 12 heating of evaporator tower 2 bottom overhead product heater vias; Material is sent into medial launder 16 after the hydrogenation reaction, and the hydrogen of gas phase after knockout drum 17 separates returns evaporator tower 2 circulation hydrogenation by recycle hydrogen press 15 and uses, and liquid phase is removed stabilizer tower 5 strippings after then flowing into medial launder 16.
Three, stripping
The material that hydrogenation operation medial launder 16 is sent here advances stabilizer tower 5 strippings, and the tower working pressure is 565KPa, and temperature is 145 ℃, by steam stripped harmful light constituent H
2S discharges off gas treatment from cat head, and benzene and toluene fraction then remove extraction process after interchanger 18 coolings at the bottom of tower.
Four, extraction
Send here through cooled benzene and toluene fraction from the stripping operation and to add from distillation tower 6 middle parts, the extraction solvent tetramethylene sulfone then adds from tower top, and distillation tower 6 adopts the tetramethylene sulfone extractive distillations, and the working pressure of extractive distillation is 140KPa, and temperature is 160 ℃.The non-aromatics gas of top of tower extraction is through the laggard separating tank 20 of interchanger 19 coolings, and phlegma is through gas-liquid separation rear section reflux column 6, and part is then removed non-aromatics product storage tank, and reflux ratio is 0.85; The bottomsstream recovery process that desolvates.
Five, solvent recuperation
The bottomsstream that extraction process is sent here enters recovery tower 7 distillations, the tower working pressure is 50KPa, temperature is 170 ℃, the aromatic hydrocarbons gas of cat head and steam are through the laggard separating tank 22 of interchanger 21 coolings, phlegma returns cat head through the gas-liquid separation rear section as phegma, it is 0.736 that part is then removed rectification working process, reflux ratio; The bottomsstream partly advances regenerator column 8 purifies, and part is then returned distillation tower 6 and made solvent usefulness, and its splitting ratio is 0.2, and the tower working pressure is 90KPa, and temperature is 180 ℃.
Six, the rectifying of purified petroleum benzin, toluene
The aromatic hydrocarbons that the solvent recuperation operation is sent here adds from benzene tower 9 middle parts, the tower working pressure is 110KPa, service temperature is 140 ℃, the cat head gas phase is through the laggard storage tank 24 of interchanger 23 coolings, the phlegma part enters benzene tower 9 as phegma, and part is then returned distillation tower 6 extractions, and reflux ratio is 2.09, tower top extraction purified petroleum benzin product, extraction toluene product at the bottom of the tower.
Seven, the rectifying of dimethylbenzene
The cut of distillation tower 1 tower middle part side line extraction is entered benzenol hydrorefining 10, the tower working pressure is 70KPa, temperature is 100 ℃, the cat head gas phase is through the laggard storage tank 26 of interchanger 25 coolings, phlegma is partly delivered to the crude benzol raw material tank, and all the other backflow benzenol hydrorefinings 10 are made trim the top of column liquid, and its reflux ratio is 100, Tata top side line extraction dimethylbenzene product, bottom extraction reorganization dispensed product storage tank.
The quality such as the following table of the character of hydrogenating materials oil, hydrogenated oil, group composition and extraction back product:
From the foregoing description 1~3 as can be seen, the present invention adopts one-stage process catalytic hydrogenation reaction (single reactor) technology, relatively suits at low pressure (2.5MPa) and lower air speed (0.75h
-1) carry out under the condition, and constant product quality, the purity height, characteristics of the present invention are to have removed heavy constituent fully in the hydrogenated oil cut of crude benzol raw material behind fore-distillation, have only benzene, toluene and non-aromatics composition, behind the hydrogenation through the products benzene of extraction process, toluene level all more than 99.9%, sulphur, nitrogen impurity content are all less than 1ppm.