CN104059691B - A kind of method of coking byproduct gasoline high-octane rating blend component - Google Patents
A kind of method of coking byproduct gasoline high-octane rating blend component Download PDFInfo
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- CN104059691B CN104059691B CN201410292122.2A CN201410292122A CN104059691B CN 104059691 B CN104059691 B CN 104059691B CN 201410292122 A CN201410292122 A CN 201410292122A CN 104059691 B CN104059691 B CN 104059691B
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Abstract
一种炼焦副产物制汽油高辛烷值调和组分的方法是将煤焦油轻油重馏分、脱酚油、重苯的炼焦副产物在加氢催化剂的固定床反应器中进行加氢反应，反应产物经冷却、气液分离后得到产物油，分离出少量的苯和重馏分，最后得汽油高辛烷值调和组分。本方法最大程度的合理利用了炼焦化学产品回收与加工过程中产生的量少、组分相似且不易于提纯分离的副产物，避免了其在常规处理使用过程中污染环境、腐蚀设备的缺点，可获得低硫、高芳的汽油高辛烷值调和组分，且有效缓解了对石油产品需求的压力。本发明是一种洁净、高附加值利用炼焦副产物来制备汽油高辛烷值调和组分的新型工艺。A method for preparing gasoline high-octane blending components from coking by-products is to carry out hydrogenation reaction of coking by-products of coal tar light oil heavy fraction, dephenolized oil and heavy benzene in a fixed-bed reactor of a hydrogenation catalyst, The reaction product is cooled and gas-liquid separated to obtain product oil, a small amount of benzene and heavy fractions are separated, and finally gasoline high-octane blending components are obtained. This method rationally utilizes the by-products produced in the recycling and processing of coking chemical products to the greatest extent, which are small in amount, have similar components and are not easy to be purified and separated, and avoid the disadvantages of polluting the environment and corroding equipment during conventional treatment and use. Low-sulfur, high-aromatic gasoline high-octane blending components can be obtained, and the pressure on the demand for petroleum products is effectively relieved. The invention is a clean and high value-added novel process for preparing gasoline high-octane blending components by using coking by-products.
Description
Technical field
The present invention relates to a kind of accord method of coking byproduct gasoline component, particularly a kind of method adopting hydroisomerisation process high added value gasoline high-octane rating blend component.
Background technology
The main composition of existing China gasoline is catalytic cracking (FCC) gasoline, its olefin(e) centent is up to 40% ~ 50%, far exceed alkene in motor spirit state V standard and be not more than the requirement of 24%, and the feature of FCC gasoline tool high-sulfur, high alkene, low virtue, not high octane value itself can be caused while the more important thing is hydrogenating desulfurization significantly to decline.In addition, along with China's coal chemical technology develops rapidly, in coking enterprise, the output of coal tar and crude benzol also improves gradually, and the utilization producing tankage in coking chemistry Product recycling and the course of processing also demonstrates not environmentally day by day, the problem such as low value-added.
In process of coking, coal tar productive rate is about 3% ~ 5% in dry coal, light oil only accounts for 0.4% ~ 0.8% in coal-tar heavy oil, and coal tar light oil is extracted hydrogen component mostly for producing benzene,toluene,xylene (BTX), and the last running of 10% is all taken as industrial fuel; Carbolic oil accounts for 1.5% in crude tar oil, and the removal phenol carbolic oil extracted after about 60% crude phenols is mainly used in producing coumarone indene resin, also has and it is directly joined in heavy fuel oil (HFO); Crude benzol productive rate is about 0.9% ~ 1.1% in dry coal, the complex mixture be made up of multiple aromatic hydrocarbons and other compounds, wherein benzene,toluene,xylene content accounts for about 90%, first crude benzol is cut into light benzene and heavy benzol in treating process, light benzene is used as the raw material of refining BTX, 10% heavy benzol is used as the raw material producing coumarone indene resin, also can do raw fuel stock or solvent oil use.The equal sulfur-bearing of three is high, and stability is poor, uses as fuel, not only causes environmental pollution and wastes again valuable resource.Produce coumarone indene resin and can produce a large amount of spent acid and salkali waste, and seriously polluted, etching apparatus, as quite serious to equipment corrosion in catalyzer boron fluoride etherate, and the health of human body is threatened, when aluminum chloride makes catalyzer, hydrogenchloride and chlorine that human body and equipment are all harmful to can be separated out in the course of the polymerization process.
Publication number is the method that the patent of CN100532509C, CN100348702C and CN101781577A represents current full fraction of coal tar hydrotreatment, all produce for the purpose of oil fuel, high, the easy coking of hydrogen consumption, etching apparatus in the hydroprocessing processes of full cut, there are various quality problems in the oil fuel produced, as produced the very low petroleum naphtha of octane value and octane value gasoline not up to standard; On the other hand, containing a variety of important industrial chemicals such as phenol, naphthalene, anthracene, carbazoles in coal tar, the value of these Chemicals is more than using large many as oil fuel, from coal tar, all do not isolate the higher Chemicals of utility value in above-mentioned disclosed patent and just directly carry out hydrotreatment, the Maxi-mize city value of coal tar is embodied, wastes valuable tar resource.Publication number is the patent of CN1147575C, CN101307257B, CN100558857C and CN102719271A is after isolating last running to coal tar, only to the method for lighting end hydrotreatment, overcome coking in full fraction of coal tar hydroprocessing processes to a certain extent and hydrogen consumes high problem, but, still there is the utilization of resources unreasonable, the problem that the gasoline of production is not up to standard.Above-mentioned patent does not accomplish abundant Appropriate application tar resource truly.
CN101538482A discloses " a kind of method of middle coalite tar deep processing ", that middle coalite tar fractionation is obtained lighting end, carbolic oil and last running, carbolic oil phenol removal, dephenolize oil carries out pyrogenic reaction jointly with last running, the at least one obtained in wherein coking naphtha, coker gas oil and wax tailings mixes with the lighting end that raw material fractionation obtains carries out hydrofining and hydrocracking reaction, the hydrotreated naphtha that hydrocracking obtains carries out catalytic reforming-Aromatics Extractive Project, obtains BTX and solvent wet goods product.Although the method improves the added value of middle coalite tar to a certain extent, be only applicable to the processing of middle coalite tar, this technique is too complicated, and coking oil product olefin(e) centent is very high, and hydrogenation hydrogen consumption also can be very high, and these will certainly increase cost.
CN101712888B discloses " a kind of heavy benzene hydrogenation process for refining ", heavy benzol mixes with hydrogen after filtering and carries out hydrofining by hydrogenation unit, obtain target product NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and solvent oil, the utilization of the method heavy benzol resource is necessarily improved, but added value of product is still on the low side.
The lightweight oil octane value that above-mentioned two patents obtain is too low, can only use as solvent oil.
In motor spirit, catalytically cracked gasoline proportion is up to 75% (massfraction), and volume fraction of olefins contained by it is 40% ~ 60%, and sulphur content is high, and hydrogenating desulfurization significantly can reduce its originally not high octane value.Refinery, in order to improve the octane value of gasoline, often adopts catalytic reforming process, and straight-chain paraffin is converted into aromatic hydrocarbons, in gasoline, add aromatic hydrocarbons, can dramatically the octane value improving gasoline.But this process need consumes mass energy, and loss part raw material.Therefore, less at the catalytic reforming unit of China, reformed gasoline ratio more American-European very low when, in order to make gasoline octane rating up to standard, the octane number additive such as methyl tertiary butyl ether (MTBE), methyl cyclopentyl-dialkyl-tricarbon manganium [M1] need be added when gasoline blending, these additives more or less all can produce detrimentally affect to engine, the more important thing is and can create environmental pollution.In today of environment protection increasingly stringent, these additives have listed the ranks be eliminated already in.
Contrast reducing of crude oil oil and cycle oil are learnt, the coking byproducts such as light oil last running, removal phenol carbolic oil, heavy benzol have the advantage that component is similar, aromaticity content is high, olefin(e) centent is low, high-octane number component is many, but it forms complexity, have a certain amount of unsaturated component, stability is poor; Also containing a certain amount of S, N, O heteroatomic compound, can etching apparatus, contaminate environment.
For above-mentioned prior art, the impurity removed wherein obtains the high fragrant blend component of gasoline high added value, not only make full use of the tankage produced in coking Product recycling and the course of processing, effectively can also alleviate the dependence of gasoline to the contour octane number additive of environmentally harmful MTBE of difficult degradation.
Summary of the invention
The deficiency existed for above-mentioned prior art and problem, the object of this invention is to provide technique simple, concentrates the method for a kind of coking byproduct gasoline high-octane rating blend component of high effect cleaning.
The object of the present invention is achieved like this, a kind of method of coking byproduct gasoline high-octane rating blend component, and method described in it is as raw material using the last running of coking byproduct light oil, dephenolize oil and heavy benzol mixing; Enter the fixed-bed reactor that hydrogenation catalyst is housed after being mixed with hydrogen by stock oil again and carry out hydrogenation reaction, make olefin saturated wherein, remove S, N, O heteroatomic compound simultaneously, the isomerization of part mononuclear aromatics, reaction product, through cooling, gas-liquid separation, obtains product oil; Gas, through separating and reclaiming hydrogen, recycles; Product oil is separated through rectifying tower, isolates a small amount of light constituent, a small amount of last running is isolated at the end and stop bracket gasoline blend component; Wherein:
Described isomerization catalyst and hydrogenation are with Al
2o
3, TiO
2, SiO
2, SiO
2-Al
2o
3, TiO
2-Al
2o
3, molecular sieve series or gac be carrier; P, N, F, B are auxiliary agent; Active ingredient is one in Ni, Co, Mo, W or its mixing.
According to technique scheme, further, additional technical feature is as follows.
Described isomerization catalyst is with Al
2o
3, TiO
2, SiO
2, SiO
2-Al
2o
3, TiO
2-Al
2o
3, molecular sieve series or gac be carrier; P, N, F, B are auxiliary agent; Active ingredient is one in Ni, Co, Mo, W or its mixing.
Described light oil last running is the cut in coal tar light oil after 170 DEG C.
Described dephenolize oil is the component of carbolic oil after proposition crude phenols in coal tar between 170 ~ 210 DEG C, or the component of dead oil after extracting crude phenols between 170 ~ 210 DEG C.
Described heavy benzol is the heavy constituent after crude benzol cuts out light benzene in treating process.
The condition of described hydrogenation is temperature: 200 ~ 460 DEG C; Pressure is: 1.0 ~ 5.0Mpa; The volume ratio of stock oil and hydrogen is: 200 ~ 1500:1, liquid air speed are: 0.2 ~ 1.8h
-1.
Realize the method for a kind of coking byproduct gasoline high-octane rating blend component provided by the present invention, compared with prior art, the advantage had and positively effect as follows.
Present method also exists for current coking byproduct and utilizes irrational problem, Appropriate application coking chemistry Product recycling and the amount that produces in the course of processing are less, component is similar and be not easy to the by product of purification & isolation, put together and passed through the inventive method, reasonable clean utilization coking byproduct to greatest extent, obtains valuable high value added product.
Present method, while raw material hydrotreated lube base oil unsaturated compound, de-S, N, O heteroatomic compound, can inhibit coming off of accordance again.
The low-octane alkylbenzene of present method isomerization part transforms to high-octane alkylbenzene.
Present method alkyl mononuclear aromatics content is high, is particularly suitable for mediation and accounts for the high alkene FCC gasoline of a high proportion of low virtue of China's motor spirit.
Present method reaction is efficient, and process stabilizing, in the reaction product obtained, sulphur content is less than 10mg/kg, and benzene content is less than 1.0%, and oxygen level is less than 2.7%, and its research octane number (RON) can, up to 110, be a kind of gasoline high-octane rating blend component of high-quality.
Embodiment
Below the specific embodiment of the present invention is further illustrated.
Implement the method for a kind of coking byproduct gasoline high-octane rating blend component provided by the present invention, the technical process of the method is as follows:
By light oil last running, removal phenol carbolic oil and heavy benzol one wherein, two kinds or three kinds be mixed to get stock oil arbitrarily; And then be mixed into hydrogen the fixed-bed reactor that hydrogenation catalyst is housed and carry out hydrogenation reaction, its operational condition is: temperature 200 ~ 460 DEG C, pressure 1.0 ~ 5.0Mpa, hydrogen-oil ratio (volume) 200 ~ 1500:1, liquid air speed 0.2 ~ 1.8h
-1; Hydrogenation products cools through interchanger, then obtains product oil through gas-liquid separator separates, and gas is through alkali liquor absorption H
2be recycled hydrogen after S, recycle; Product oil is separated through rectifying tower, isolates a small amount of light constituent, a small amount of last running is isolated at the end and stop bracket gasoline blend component.In the reaction product obtained, sulphur content is less than 10mg/kg, and benzene content is less than 1.0%, and oxygen level is less than 2.7%, and its research octane number (RON) can up to 110.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Hydrogenation catalyst used in embodiment with porous refractory thing for carrier, containing group vib element, group VIIIB element.Group vib constituent content 13% ~ 28%(presses oxide basis), group VIIIB constituent content 2% ~ 8%(presses oxide basis), boron, nitrogen, fluorine, phosphorus content 0% ~ 5.5%.
The principal reaction that present method relates to mainly contains:
(1) the sulfocompound desulfurization of thiophene-based
(2) the oxygenatedchemicals deoxidation of phenol, coumarone class
(3) the compound denitrogenation of pyridine, pyrroles and quinoline
(4) hydrogenation of unsaturated hydrocarbons:
(5) isomerization reaction of alkylbenzene
Embodiment 1
Light oil last running and removal phenol carbolic oil are mixed to get stock oil with the ratio of 2:5, enter in the fixed-bed reactor that hydrogenation catalyst is housed after stock oil mixes with hydrogen and carry out hydrogenation reaction, optimum hydrogenation conditions: temperature is 260 ~ 340 DEG C, pressure is 2.4 ~ 3.6Mpa, hydrogen-oil ratio (volume) is 650 ~ 850:1, liquid air speed is 0.9 ~ 1.0h
-1; Reaction product cools through interchanger, then obtains through gas-liquid separator separates, and gas is through alkali liquor absorption H
2hydrogen is recycled after S; Hydrogen recycle uses; Product oil is separated through rectifying tower, and tower top isolates the light constituent based on benzene, obtains last running at the bottom of tower, and gasoline high-octane rating blend component isolated by side line.According to material trend in fixed-bed reactor, raw material, successively through two kinds of hydrogenation catalysts, is respectively the CoMo/ of P modification
η-Al
2o
3and Ni/ZSM-5, both volume ratios are 5:1, and gasoline high-octane rating blend component character is in table 1.
Embodiment 2
Three mixed removal phenol carbolic oils and heavy benzol are mixed into stock oil with the ratio of 1:3, enter in the fixed-bed reactor that hydrogenation catalyst is housed after stock oil mixes with hydrogen and carry out hydrogenation reaction, optimum hydrogenation conditions: temperature is 330 ~ 420 DEG C, pressure is 4.0 ~ 4.6Mpa, hydrogen-oil ratio (volume) is 1200 ~ 1400:1, liquid air speed is 0.2 ~ 1.0h
-1; Reaction product cools through interchanger, then obtains different oil through gas-liquid separator separates, and gas is through alkali liquor absorption H
2hydrogen is recycled after S; Hydrogen recycle uses; Product oil is separated through rectifying tower, and tower top isolates the light constituent based on benzene, obtains last running at the bottom of tower, and gasoline high-octane rating blend component isolated by side line.According to material trend in fixed-bed reactor, raw material, successively through two kinds of hydrogenation catalysts, is respectively WoMo/ gac and the WNi/ of N modification
β-zeolite, both volume ratios are 4.5:1, and gasoline high-octane rating blend component character is in table 1.
Embodiment 3
Light oil last running and heavy benzol are mixed into stock oil with the ratio of 1:2, enter in the fixed-bed reactor that hydrogenation catalyst is housed after stock oil mixes with hydrogen and carry out hydrogenation reaction, optimum hydrogenation conditions: temperature is 270 ~ 390 DEG C, pressure is 1.8 ~ 3.8Mpa, hydrogen-oil ratio (volume) is 650 ~ 1500:1, liquid air speed is 0.2 ~ 1.2h
-1; Reaction product cools through interchanger, then obtains oil through gas-liquid separator separates, and gas is through alkali liquor absorption H
2hydrogen is recycled after S; Hydrogen recycle uses; Product oil is separated through rectifying tower, and tower top isolates the light constituent based on benzene, obtains last running at the bottom of tower, and gasoline high-octane rating blend component isolated by side line.According to material trend in fixed-bed reactor, raw material, successively through two kinds of hydrogenation catalysts, is respectively the NiMo/TiO of F modification
2-Al
2o
3with F modification W/ mordenite, both volume ratios are 3:1, and stop bracket gasoline blend component character is in table 1.
Embodiment 4
Light oil last running, two mixed removal phenol carbolic oils and heavy benzol are mixed into stock oil with the ratio of 1:1:2, enter in the fixed-bed reactor that hydrogenation catalyst is housed after stock oil mixes with hydrogen and carry out hydrogenation reaction, optimum hydrogenation conditions: temperature is 270 ~ 420 DEG C, pressure is 2.2 ~ 4.2Mpa, hydrogen-oil ratio (volume) is 650 ~ 1000:1, liquid air speed is 0.2 ~ 1.2h
-1; Reaction product cools through interchanger, then obtains isomerate feeds oil through gas-liquid separator separates, and gas is through alkali liquor absorption H
2be recycled hydrogen after S, hydrogen recycle uses; Product oil is separated through rectifying tower, and tower top isolates the light constituent based on benzene, obtains last running at the bottom of tower, and gasoline high-octane rating blend component isolated by side line.According to material trend in fixed-bed reactor, raw material, successively through two kinds of hydrogenation catalysts, is respectively the CoMo/SiO of B modification
2-Al
2o
3with F modification W/SiO
2-Al
2o
3, both volume ratios are that 6:1 gasoline high-octane rating blend component character sees the above table 1.
Claims (4)
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| CN101633848B (en) * | 2009-08-31 | 2012-11-21 | 中煤能源黑龙江煤化工有限公司 | Method for further processing medium and low temperature coal tar |
| FR2966160B1 (en) * | 2010-10-14 | 2013-11-15 | IFP Energies Nouvelles | CATALYTIC CRACKING METHOD FOR PROCESSING LOW CARBON CONRADSON LOADS COMPRISING THE RECYCLING OF A CUTTING CUTTING ACCORDING TO A NEW TECHNOLOGY |
| CN102851073B (en) * | 2012-08-27 | 2014-08-13 | 王小英 | Medium and low temperature combination processing method of coal tar |
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