Method by C+10 heavy aromatic hydrocarbon feedstock production petronaphthalene
Technical field
The invention belongs to the preparing technical field of petronaphthalene, be specifically related to a kind of method by C+10 heavy aromatic hydrocarbon feedstock production petronaphthalene.
Background technology
NAPTHALENE FLAKES. (INDUSTRIAL GRADE is a kind of broad-spectrum fine chemical product, for industries such as weaving, printing and dyeing, papermaking crucial meaning is arranged.
Naphthalene (Naphthalene) molecular formula C
10H
8, molecular weight 128 is the simplest a kind of condensed nucleus aromatic compounds with two adjacent aromatic nucleus.Card (Carden) finds at first that in 1820 it is present in the coal tar distillate.The structural formula of naphthalene is write as usually:
1,4,5,8 positions are called the α position, and 2,3,6,7 positions are called the β position.
Naphthalene is solid at normal temperatures, is sublimed into colourless flap or monoclinic crystal easily.Thick naphthalene has sharp aroma owing to contain impurity, and high-purity no sulphur naphthalene has gentle aromatic odour.Naphthalene burns in air has a large amount of black smokes to generate.The main physical and chemical performance of naphthalene is as follows: 218 ℃ of boiling points; 80.29 ℃ of fusing points; 78.89 ℃ of flash-points (remaining silent); Be slightly soluble in water; Can be dissolved in multiple organic solvent.
Naphthalene is present in the coal-tar heavy oil fraction, in the petroleum cuts and some natural aromatic oil after reforming.Up to 20th century the fifties, unique source of naphthalene is still the coal tar that coal obtains in the high-temperature coking process, and the initial stage in the sixties, the U.S. developed by preparing NAPTHALENE FLAKES. (INDUSTRIAL GRADE in the petroleum.The source of China's NAPTHALENE FLAKES. (INDUSTRIAL GRADE mainly is the by product-coal tar of coking at present, and the quality standard relevant with naphthalene all is tar naphthalene quality standard, do not have the quality standard of petronaphthalene so far.
The production method of tar naphthalene has two kinds:
A) crystallization milling process, and the crystallization milling process is divided into two kinds of intermittent type and continous ways, the former technological process is crystallization, centrifugation and squeezing; The latter directly enters the horizontal drum crystallizer of airtight steel with the naphtalene oil after the dephenolize, in establish spiral stirrer.The cooling of outer wall water spray makes naphthalene crystal.The crystallization material is sent into squeezing machine and is squeezed into the naphthalene cake after centrifugation, be easy to separate for making oil content and naphthalene, and squeezing is carried out under 50~55 ℃.A complete set of press apparatus is made up of agitator, naphthalene press, hydro-pump, pressure accumulator and steering hand wheel etc.The refining rate of this technology required equipment heaviness and maintenance rate height, especially naphthalene only is 83~93%.
The continuous crystallisation squeezing legal system naphthalene technology of Germany Kopper company and Gelsenkirchener company is: naphtalene oil crystallisation by cooling on cooling roller is entered hopper by the section back by chute again.Enter the continuously spiral squeezing machine then and squeeze, the product that ctystallizing point is 78 ℃ sprays at squeezing machine front end nozzle.The Residual oil separated into two parts that squeezing is discharged.The amount of Residual oil sulfur-bearing, the indenes of squeezing front end is higher, and naphthalene content is low, therefore is exhausted from system.The Residual oil in squeezing stage casing enters distillation tower, cuts behind the washing oil fraction to contain the high naphtalene oil of naphthalene with the squeezing back segment and mix and return in the raw material, and the refining rate of naphthalene only is 80% like this.
B) distillation method, this method are in view of crystallization milling process complex process equipment, and the refining rate of naphthalene is low and release after the seventies in 20th century, and this method handles the NAPTHALENE FLAKES. (INDUSTRIAL GRADE that naphtalene oil production contains naphthalene amount 〉=95%.Big or small available intermittent type or continous way distillation according to production capacity.The domestic and international twin furnace double tower method that adopts morely.
Aforesaid method is because the raw material that uses is coal tar, quite complicated and need pyroprocessing and cause that naphthalene impurity is more, the color and luster jaundice in view of the composition of coal tar, therefore also need sulfuric acid scrubbing or hydrofining to be purified, not only environmental pollution is serious, technical process is long but also cost is high.
Summary of the invention
Task of the present invention is that a kind of method by C+10 heavy aromatic hydrocarbon feedstock production petronaphthalene will be provided, petronaphthalene with this method preparation need not to carry out further refining, not only technology is simple, and do not undermine environment, can embody simultaneously the comprehensive utilization of resource, product color is good, purity is high, no abnormal smell and can reach the Quality of Naphthalene standard.
Task of the present invention is finished like this, a kind of method by C+10 heavy aromatic hydrocarbon feedstock production petronaphthalene, it is that the C+10 heavy aromatic hydrocarbon raw material that will hang down naphthalene content earlier is incorporated into rectifying the rectifying tower from the opening for feed of first rectifying tower before being incorporated into first rectifying tower by pipeline with after the cat head light fraction overhead product heat exchange of first rectifying tower, control the tower top temperature of first rectifying tower, tower top pressure, Heating temperature at the bottom of reflux ratio and the tower, the cat head light fraction is after heat exchange and condensation, phlegma enters return tank of top of the tower, overhead product is that first solvent is drawn by pipeline, the first side line pipeline of first rectifying tower leads to the durol pregnant solution, after branch removes light fraction overhead product and durol pregnant solution, heavy fraction overhead product at the bottom of the tower introduced in second rectifying tower continue rectifying, control the tower top temperature of second rectifying tower, tower top pressure, Heating temperature at the bottom of reflux ratio and the tower, the second rectifying tower overhead product is that second solvent is drawn by pipeline, in second rectifying tower, divide and go gently, the heavy fraction overhead product is after the second side line pipeline of second rectifying tower is drawn the naphthalene pregnant solution, the naphthalene pregnant solution separates crystalline mother solution with centrifugal separating device behind the crystallization apparatus crystallisation by cooling, obtains the finished product petronaphthalene.
A kind of method by C+10 heavy aromatic hydrocarbon feedstock production petronaphthalene, it is earlier the C+10 heavy aromatic hydrocarbon raw material of high naphthalene content to be incorporated into rectifying in the rectifying tower by the opening for feed of rectifying tower, and Heating temperature at the bottom of control tower top temperature, tower top pressure, reflux ratio and the tower, go gently at branch, obtain the liquid naphthalene behind the overhead product of heavy fraction, again the liquid naphthalene is incorporated into liquid naphthalene storage tank from the lateral line canal road of rectifying tower, or directly send into flaker knot sheet, obtain the finished product petronaphthalene.
In a specific embodiment of the present invention, described low naphthalene content is meant that the content of naphthalene is 3-7%, and the temperature after described C+10 heavy aromatic hydrocarbon raw material and the heat exchange of cat head light fraction overhead product is 50~70 ℃.
In another specific embodiment of the present invention, the tower top temperature of described control first rectifying tower is for to be controlled to be 110~130 ℃ with temperature, the tower top pressure of described control first rectifying tower is that the cat head absolute pressure is controlled to be 15~20KPa, the reflux ratio of described control first rectifying tower be with control of reflux ratio at 1: 6~1: 12, Heating temperature is that the temperature of the heating medium thermal oil of well heater at the bottom of the control tower is at 270~295 ℃ at the bottom of the tower of described control first rectifying tower.
Go back in the specific embodiment of the present invention, described first solvent is 1000
#Solvent, and described second solvent is 1500
#Solvent.
In another specific embodiment of the present invention, the tower top temperature of described control second rectifying tower is that temperature is controlled to be 120~130 ℃, the tower top pressure of described control second rectifying tower is that the cat head absolute pressure is controlled to be 10~15KPa, and the reflux ratio of described control second rectifying tower is at 1: 6~1: 12 with control of reflux ratio.
In another specific embodiment of the present invention, the temperature of described naphthalene pregnant solution is that 130~140 ℃, naphthalene content are 50-65%.
More of the present invention and in specific embodiment, described crystallization apparatus is the crystallisation by cooling still, and heat-eliminating medium is 18~25 ℃ a recirculated water, and circulation cooling time is 6~10h, described centrifugal separating device is a filtering centrifuge, and the rotating speed of whizzer is 1300~1500r/min.
Of the present invention again more and in specific embodiment, described high naphthalene content is meant that the content of naphthalene is 25~35%.
In of the present invention and then specific embodiment, described control rectifying tower tower top temperature is that tower top temperature is controlled to be 110~120 ℃, described control tower top pressure is that the cat head absolute pressure is controlled to be 10~15KPa, described control reflux ratio for the control reflux ratio at 1: 6~1: 12, Heating temperature is that the temperature of the heating medium thermal oil of well heater at the bottom of the control tower is at 270~295 ℃ at the bottom of the tower of described control rectifying tower.
Method processing step disclosed by the invention is few, easy and simple to handle; Owing to utilized the C+10 heavy aromatic hydrocarbon that is often used as fuel, therefore not only raw material sources easily and belong to the comprehensive utilization of C+10 heavy aromatic hydrocarbon, so cost is low; Preparation process carries out and need not purifying in enclosed system, does not therefore have the three wastes factor that undermines environment.
Description of drawings
Fig. 1 is the used schematic representation of apparatus of embodiments of the invention 1-4.
Fig. 2 is the used schematic representation of apparatus of embodiments of the invention 5-8.
Embodiment
Embodiment 1:
Ask for an interview accompanying drawing 1, to be 3% C+10 heavy aromatic hydrocarbon raw material available from the naphthalene amount that contains in the Sinopec Yangzi Petrochemical Group Limited company of NanJing City, Jiangsu Province,China Liuhe District, be 1.6m by pipeline 1 tying-in diameter at normal temperatures, tower height is 35m, stage number be 138 first rectifying tower 2 the first cat head interchanger 3 with come from first rectifying tower, 2 cats head and light fraction overhead product heat exchange that enter into the first cat head interchanger 3, temperature is introduced rectifying first rectifying tower 2 at 68 ℃ C+10 heavy aromatic hydrocarbon raw material from the tower body middle and lower part opening for feed of first rectifying tower 2 after heat exchange is promptly absorbed heat.The rectifying condition is controlled to be: the first column overhead temperature is that 130 ℃, cat head absolute pressure are 19KPa, the first rectifying tower cat head light fraction overhead product is after the heat exchange cooling, phlegma enters in first return tank of top of the tower 4 of first rectifying tower 2, first overhead condenser 5 that uncooled part enters first rectifying tower 2 enters in first return tank of top of the tower 4 of first rectifying tower 2 through further condensed liquid, and the control reflux ratio is 1: 7.First solvent of drawing 80 ℃ through first pipeline 6 is 1000
#Solvent, the first side line pipeline 7 of first rectifying tower 2 is drawn the durol pregnant solution, at the bottom of the tower of first rectifying tower 2 heavy fraction enter well heater at the bottom of first Tata promptly first reboiler 8 through 295 ℃ heat-conducting oil heating, forming the circulation heating evaporation returns at the bottom of the tower of first rectifying tower 2 light constituent that wherein contains, it is 1.8m that the heavy fraction of first rectifying tower 2 is introduced diameter by the first tower bottom tube road 9, tower height is 35m, stage number is that the middle and lower part opening for feed of 130 second rectifying tower 10 enters second rectifying tower 10 and carries out rectifying, the tower top temperature of second rectifying tower 10 is controlled to be 122 ℃, control of reflux ratio is 1: 6, and the cat head absolute pressure is controlled to be 11Kpa.The light fraction of second rectifying tower 10 enters second return tank of top of the tower 12 through the second cat head interchanger, 11 cooled liquid, uncooled part enters further condensation in second overhead condenser 13 of second rectifying tower 10, phlegma enters in second return tank of top of the tower 12 of second rectifying tower 10, draws second solvent through second pipeline 14 and is 1500
#Solvent.The heavy fraction of second rectifying tower 10 enter well heater at the bottom of the tower of second tower promptly second reboiler 15 through 276 ℃ heat-conducting oil heating, form the circulation heating evaporation light constituent that wherein contains is returned at the bottom of the tower of second rectifying tower 10, the heavy fraction overhead product leads to subsequent processing through the second tower bottom tube road 16 and further processes at the bottom of the tower of second rectifying tower 10.In second rectifying tower 10, divide and go that resultant temperature is 130 ℃ behind light, the heavy fraction overhead product, to contain the naphthalene amount that to be 52% naphthalene pregnant solution be incorporated in the crystallization kettle 18 by the second side line pipeline 17 of second rectifying tower, 10 middle and upper parts, the naphthalene pregnant solution in crystallization kettle 18 by temperature be 25 ℃ recirculated water cooling 7.5h after pipeline introduce in the filtering centrifuge 19, speed with 1500r/min is sloughed crystalline mother solution, obtains petronaphthalene finished product 20.For whizzer 19, preferred but be not limited to the LML350 type horizontal screw unloading filter formula whizzer that the Sino-Foreign Joint Venture Zhangjiagang Huada Centrifuger Mfg. Co., Ltd by the Zhangjagang City, Jiangsu Province, China produces.Through the finished product petronaphthalene is analyzed, purity is 95.1%.
Embodiment 2:
Only the content of naphthalene in the C+10 heavy aromatic hydrocarbon raw material is changed into the cat head distilled 1000 of 7%, the first rectifying tower 2
#Solvent temperature changes 71 ℃ into, the temperature of the C+10 heavy aromatic hydrocarbon raw material after heat exchange is promptly absorbed heat changes 52 ℃ into, first rectifying tower, 2 control conditions: tower top temperature changes that 112 ℃, reflux ratio change 1: 10 into, the cat head absolute pressure changes 15KPa into into, and the heat-conducting oil heating temperature changes 280 ℃ at the bottom of the tower; Second rectifying tower, 10 control conditions: tower top temperature changes 130 ℃ into, the control reflux ratio changes 1: 9 into, the cat head absolute pressure changes 15Kpa into, the temperature of the naphthalene pregnant solution that the second side line pipeline 17 is drawn changes 134 ℃ into, contain the naphthalene amount changes 60% into, the recirculated cooling water temperature changes 22 ℃ into, change 9h cooling time into, the rotating speed of filtering centrifuge 19 changes 1400r/min into, and all the other are with the description to embodiment 1.Through the finished product petronaphthalene is analyzed, purity is 98.7%.
Embodiment 3:
Only the content of naphthalene in the C+10 heavy aromatic hydrocarbon raw material is changed into the cat head distilled 1000 of 5.9%, the first rectifying tower 2
#Solvent temperature changes 76 ℃ into, the temperature of the C+10 heavy aromatic hydrocarbon raw material after heat exchange is promptly absorbed heat changes 61 ℃ into, and first rectifying tower, 2 control conditions: tower top temperature changes 121 ℃ into, and reflux ratio changes 1: 12 into, the cat head absolute pressure changes 17KPa into, and the heat-conducting oil heating temperature changes 272 ℃ at the bottom of the tower; Second rectifying tower, 10 control conditions: tower top temperature changes 126 ℃ into, the control reflux ratio changes 1: 10 into, the cat head absolute pressure changes 13KPa into, the temperature of the naphthalene pregnant solution that the second tower side line pipeline 17 is drawn changes 136 ℃ into, contain the naphthalene amount changes 65% into, the recirculated cooling water temperature changes 20.5 ℃ into, change 6h cooling time into, the rotating speed of filtering centrifuge 19 changes 1300r/min into, and all the other are with the description to embodiment 1.Through the finished product petronaphthalene is analyzed, purity is 97.9%.
Embodiment 4:
Only the content of naphthalene in the C+10 heavy aromatic hydrocarbon raw material is changed into the cat head distilled 1000 of 4.6%, the first rectifying tower 2
#Solvent temperature changes 78 ℃ into, the temperature of the C+10 heavy aromatic hydrocarbon raw material after heat exchange is promptly absorbed heat changes 65 ℃ into, and first rectifying tower, 2 control conditions: tower top temperature changes 129 ℃ into, and reflux ratio changes 1: 8 into, the cat head absolute pressure changes 20KPa into, and the heat-conducting oil heating temperature changes 285 ℃ at the bottom of the tower; Second rectifying tower, 10 control conditions: tower top temperature changes 125 ℃ into, the control reflux ratio changes 1: 8 into, the cat head absolute pressure changes 12KPa into, the temperature of the naphthalene pregnant solution that the second side line pipeline 17 is drawn changes 139 ℃ into, contain the naphthalene amount changes 57% into, the recirculated cooling water temperature changes 18.5 ℃ into, change 10h cooling time into, the rotating speed of filtering centrifuge 19 changes 1350r/min into, and all the other are with the description to embodiment 1.Through the finished product petronaphthalene is analyzed, purity is 98.1%.
Embodiment 5:
Ask for an interview accompanying drawing 2, the naphthalene amount that contains that to discuss square 26A5 of luxuriant century Nanjing source of a specified duration petrochemical industry company limited for No. 49 and provide available from south of the mountains road in the NanJing City, Jiangsu Province,China is 25% C+10 heavy aromatic hydrocarbon raw material, be 1.8m by pipeline 1 from diameter at normal temperatures, tower height is 35m, stage number is that the middle and lower part opening for feed introducing rectifying tower 2 of 112 rectifying tower 2 carries out rectifying, condition is controlled to be: reflux ratio is 1: 10, the cat head absolute pressure is 10KPa, tower top temperature is 112 ℃, the light fraction of rectifying tower 2 liquid after 3 coolings of cat head interchanger enters in the return tank of top of the tower 4, uncooled part enters further condensation in the overhead condenser 5 of rectifying tower 2, phlegma enters in the return tank of top of the tower 4 of rectifying tower 2, and overhead product is 1500
#Solvent is by drawing through pipeline 6.To enter well heater at the bottom of the tower be reboiler 7 to heavy fraction through 295 ℃ heat-conducting oil heating at the bottom of the tower, form the circulation heating evaporation lighting end that wherein contains is returned at the bottom of the tower of rectifying tower 2, the heavy fraction overhead product is drawn subsequent processing through tower bottom tube road 8 and is further processed at the bottom of the tower of rectifying tower 2.Divide in rectifying tower 2 and go that the resulting naphthalene amount that contains is that 97.0% liquid naphthalene is incorporated into liquid naphthalene tundish 10 by side line pipeline 9 behind light, the heavy fraction overhead product, the liquid naphthalene draws or enters directly that the knot sheet makes petroleum coal naphthalene 13 in the flaker 12 through introduction pipe 11.
Embodiment 6:
Only the content with naphthalene in the C+10 heavy aromatic hydrocarbon raw material changes 30% into, and rectifying tower 2 control reflux ratios change 1: 10 into, and the cat head absolute pressure changes 13KPa into, and tower top temperature is 119 ℃, and the Heating temperature of tower bottom reboiler 7 changes 295 ℃ into, and all the other are with the description to embodiment 5.Through the finished product petronaphthalene is analyzed, purity is 98.8%.
Embodiment 7:
Only the content with naphthalene in the C+10 heavy aromatic hydrocarbon raw material changes 27.5% into, and rectifying tower 2 control reflux ratios change 1: 8 into, and the cat head absolute pressure changes 15KPa into, and tower top temperature is 120 ℃, and the Heating temperature of tower bottom reboiler 7 changes 280 ℃ into, and all the other are with the description to embodiment 5.Through the finished product petronaphthalene is analyzed, purity is 97.6%.
Embodiment 8:
Only the content with naphthalene in the C+10 heavy aromatic hydrocarbon raw material changes 33% into, and rectifying tower 2 control reflux ratios change 1: 7 into, and the cat head absolute pressure changes 12KPa into, and tower top temperature is 115 ℃, and the Heating temperature of tower bottom reboiler 7 changes 285 ℃ into, and all the other are with the description to embodiment 5.Through the finished product petronaphthalene is analyzed, purity is 98.6%.
By the foregoing description as seen, in the process by C+10 heavy aromatic hydrocarbon feedstock production petronaphthalene, except that petronaphthalene finished product packing workshop section, other processes all are under the air tight condition carries out, and this has not only improved utilization ratio of raw materials greatly and simultaneously environment and operator has not been exerted an influence.