CN105316018A - Pretreatment method for deep processing of coal tar - Google Patents
Pretreatment method for deep processing of coal tar Download PDFInfo
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- CN105316018A CN105316018A CN201410384926.5A CN201410384926A CN105316018A CN 105316018 A CN105316018 A CN 105316018A CN 201410384926 A CN201410384926 A CN 201410384926A CN 105316018 A CN105316018 A CN 105316018A
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Abstract
The invention relates to a pretreatment method for deep processing of coal tar. A technology for carrying out deslagging, ammonia water removing, dephenolizing and desalting separation on the coal tar through centrifugal separation, gas backwashing filtering, distilling and high-voltage electric field is adopted, the pretreatment method is applicable to the pretreatment of high-temperature coat tar, medium-temperature coal tar and low-temperature coat tar, the separated ammonia water can be recycled, and phenols are sold as a chemical raw material directly or after the phenols are refined, so that the problems that wastewater containing ammonia and phenol is discharged, a hydrogen source of energy is wasted due to phenol hydrogenation, and the like are avoided, and the added value of the coal tar is increased.
Description
Technical field
The present invention relates to a kind of pretreatment process of coal tar raw material, especially a kind of coal tar deep processing pretreatment process, belongs to chemical technology field.
Background technology
Along with the crisis of petroleum resources, the approach seeking new oil product resource becomes the focus of people's concern, and therefore coal tar processing industry causes the attention of people once again.Except traditional coal tar processing product developments such as such as naphthalene, anthracene, phenols and pitch have gone out new purposes, the coal-tar products processed further by hydrotreatment becomes the product having more the market competitiveness.
Coal tar hydrogenating is produced light Fuel oil tech and is developed faster, reasonably processing and utilization coal tar, the demand of various industrial chemicals not only can be provided, and petroleum resources pressure in short supply can be alleviated, increase added value of product and expand product structure extension.
Applicant retrieves discovery, application number be 200910045839.6 Chinese patent application disclose a kind of coal tar coupled rotational flow purification method, the method comprises the following steps: coal tar fully mixes with trapping agent by (a), to extract the salinity disperseed in coal tar; B () carries out liquid-liquid rotational flow separation to the coal tar having extracted the salinity wherein disperseed, to isolate salinity, obtain desalination coal tar; C () carries out standing sedimentation to desalination coal tar, to remove moisture wherein, obtain dehydrated coal tar; D () carries out solid-liquid rotational flow separation to dehydrated coal tar, to remove solid particulate wherein, obtain the coal tar being stripped of solid particulate; And (e) carries out mini-hydrocyclone separation to the coal tar being stripped of solid particulate, to remove micro-moisture wherein.Its Problems existing is: the complex mixture that coal tar is made up of polar material and apolar substance, existing Van der Waals force between molecule, also there is hydrogen bond, cyclonic separation can only partly isolate imperfect material, phenols and water also can form hydrogen bond, therefore, water in coal tar is difficult to be removed by cyclonic separation, coal ash sticks on tar in addition, density is relatively little also cannot pass through cyclonic separation, ammonia is contained in addition in isolated water, the materials such as phenols, contaminate environment, first the present invention passes through centrifugation, mechanical impurity removes by filters, 10 μm of decreasing ratiies are made to reach 98%, secondly deammoniation is removed through distillation, water, phenols, last then carry out secondary or the salinity in coal tar removes by three grades of Crude Desalting Systems, moisture residual in coal tar removes through flash distillation.Application number be 200910048881.3 Chinese patent disclose coalite tar deep processing method in one, the method carries out fractionation by after the raw materials pretreatment of middle low temperature coal tar, obtain lighting end, carbolic oil and last running, carbolic oil carries out phenol removal, obtain phenol products and dephenolize oil, this dephenolize oil carries out pyrogenic reaction jointly with step aforesaid heavy fractions, obtain various coking product, wherein coking naphtha, at least one in 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, obtain benzene, toluene, dimethylbenzene and solvent wet goods product.Its shortcoming is that centrifuging, electrodesalting and electrodehydrating are mentioned in coal tar pre-treatment, centrifuging only removes most of mechanical impurity, phenols, ammonia still exist in coal tar, cause the easy emulsification coal tar of coal tar to be divided into five layers in electric desalting tank body: light oil, light oil and emulsifying water layer, water layer, water and heavy oil emulsive layer, heavy oil; Make electric desalting cannot steady running, electric desalting draining enriched ammonia, phenol, contaminate environment.In application number coal tar pretreatment technology and suite of equipment disclosed in the Chinese patent of 200910224893.7, the pretreated operational path of coal tar is: heat sinkly in feed coal tar tank fall → raw oil pump conveying → ultra centrifugal separation → interchanger intensification → strainer removal of impurities → one-stage water wash electric field separates → secondary washing electric field separates → pre-treatment corrected oil deep processing.This patent and 200910048881.3 pre-treatment similar, only before centrifugation, particularly point out sedimentation in hot slurry tank, in slurry tank, only can deviate from a part of ammoniacal liquor and a small amount of impurity.Application number be 201210007868.5 Chinese patent application disclose the full cut method of comprehensive utilization of a kind of coal tar hydrogenating combinatorial delays coking, the method comprises coal tar pre-treatment, coal tar high efficiency separation, heavy ends delayed coking and fixed bed hydrogenation four unit, the finished product are the fine chemicals such as phenol, naphthalene, gasoline, diesel oil, pitch coke, and operation steps is as follows:
(1) at coal tar pretreatment unit, pending raw material full distillate oil through dewatering, dedusting, desalination purifying treatment, enter next unit, (2) at coal tar high efficiency separation unit, pretreated coal tar enters separation column, fractionate out the carbolic oil cut of 170 ~ 210 DEG C and the fraction of naphthalene oil of 210 ~ 230 DEG C, carbolic oil and naphtalene oil refine to obtain fine chemicals phenol and naphthalene further, the light oil distillate that < is 170 DEG C removes fixed bed hydrogenation unit, and residue cut removes heavy ends delayed coking unit, (3) at heavy ends delayed coking unit, delayed coking charging is the coal tar fraction of > 230 DEG C, delayed coking product is light-weight fuel oil and pitch coke, and pitch coke is as the finished product, and light-weight fuel oil enters fixed bed hydrogenation unit, (4) at fixed bed hydrogenation unit, the light oil distillate that coal tar < is 170 DEG C, carbolic oil and naphtalene oil refine after residue cut and the mixing of delayed coking light-weight fuel oil as the raw material of hydrogenation, hydrogenated products obtain the finished product gasoline and diesel oil through rectifying, first a small amount of this patent of tail oil circulation hydrogenation is by after cyclonic separation dedusting, then dehydration tower dehydration is entered, after dehydration, coal tar enters separation column, desalting treatment is mentioned in summary of the invention, the method of desalting treatment facility and concrete desalination is not had in schema, dehydration and tar separation are carried out in two towers in addition, add the input of equipment, through coking before hydrogenation, part of coal tar is made to become burnt, coal tar comprehensive utilization ratio is not high.
Summary of the invention
The object of the invention is to: propose one and can make full use of raw material, establish ideal basic for hydrotreatment, effectively avoid the coal tar deep processing pretreatment process of chemical pollution simultaneously.
Owing to containing a large amount of ammoniacal liquor, salt and solid impurity in coal tar, coal tar and the water capacity easily form stable emulsion, in addition, ammonium salt can resolve into free acid and ammonia, cause the heavy corrosion of pipeline and equipment, solid impurity is fine breeze, coke powder and carbon powder etc. mainly, and these solid impurities meeting blocking pipe, therefore needed to carry out purifying treatment to coal tar before coal tar deep processing.
Applicant is found by research, after removing mechanical impurity, first ammoniacal liquor, the aldehydes matter in coal tar should be removed before electric desalting, because tarry cut and water generation emulsification can be made containing a large amount of ammoniacal liquor in coal tar on the one hand, on the other hand, phenolic component can form hydrogen bond with coal Semi-polarity functional group (such as water-OH), make that electrodesalting and electrodehydrating effect is poor does not reach index, and the sewage of discharging contains a large amount of phenols, ammonia, contaminate environment, phenols can produce water again in hydrogenation process, waste hydrogen.On above-mentioned Research foundation, in order to reach above object, coal tar deep processing pretreatment process of the present invention, comprises the following steps:
The first step, centrifugation---be separated the solid impurity in coal tar by whizzer, make wherein contained solid grain size be less than 50 μm;
Second step, filtering separation---by the solid impurity in the further filtering separation coal tar of filtering material, make more than 15 μm wherein contained solids removal rates more than 98%;
3rd step, by the coal tar heating after centrifugal and filtering separation, distillation cuts out ammoniacal liquor, light oil, carbolic oil, ammoniacal liquor and carbolic oil is processed further, carbolic oil directly or after refining as industrial chemicals, by isolated light constituent, (density 20 DEG C, is not more than 0.98g/cm
3), the mixing of dephenolize oil adds water, metal remover, emulsion splitter mix through static mixer; Remaining heavy constituent adds water, metal remover, emulsion splitter mix through static mixer;
4th step, by light constituent and heavy constituent mixed solution respectively through two-stage or three grades of electrodesalting and electrodehydrating process, remove salt, water and tiny mechanical impurity;
5th step, by the light constituent after electric desalting, heavy constituent respectively distillation dehydration, its water ratio is made to be less than 0.05%; Or make its water ratio be less than 0.05% light, heavy constituent mixing distillation dehydration;
6th step, hydrogenation unit is removed in light, the heavy constituent mixing after the 5th step dehydration.
Above method adopts and removes mechanical impurity, and distillation except ammonia and phenols, then carries out desalting and dewatering method, decreases corrosion and environmental pollution, improves the comprehensive utilization ratio of coal tar.In described second step, filter type is that gas back-flushing filters.
In described 3rd step, distill the ammoniacal liquor that obtains and reclaimed by conventional acid wash, generate ammonium sulfate, the phenols that carbolic oil obtains through conventional acid soda finishing, as industrial chemicals, avoids waste hydrogen, the reluctant problem of phenolic wastewater.
In the 4th described step by light constituent and heavy constituent mixed solution respectively through two-stage or three grades of electrodesalting and electrodehydrating process, remove salt, water and tiny mechanical impurity, reaching the requirement of hydrogenating materials through the 5th step;
The present invention mainly by coal tar fractional distillation----electrodesalting and electrodehydrating----hydrogenation produce light-weight fuel oil and other Chemicals.Centrifugation, gas back-flushing filtration, distillation, high-voltage electric field is adopted coal tar to be carried out to the technology of de-slag, deamination water, dephenolize, desalination separation, be applicable to the pre-treatment of coal-tar heavy oil, coal-tar middle oil and coalite tar, isolated ammoniacal liquor can be recycled, phenols directly or after refining is sold as industrial chemicals, avoid containing ammonia, phenol discharge of wastewater, the problems such as phenol hydrogenation waste hydrogen energy source, improve the added value of coal tar.
Embodiment
The coal tar deep processing pretreatment process of the present embodiment, comprises the following steps:
The first step, centrifugation---be separated the solid impurity in coal tar by whizzer, make wherein contained solid grain size be less than 50 μm;
Second step, filtering separation---by the solid impurity in the further filtering separation coal tar of filtering material, make more than 15 μm wherein contained solids removal rates more than 98%;
3rd step, by the coal tar heating after centrifugal and filtering separation, distill out ammoniacal liquor, light oil, carbolic oil, ammoniacal liquor and carbolic oil are processed further, carbolic oil refine after dephenolize oil and heavy constituent mix, add water, metal remover, emulsion splitter mix through static mixer;
4th step, by dephenolize oil and heavy constituent mixed solution through two-stage or three grades of electrodesalting and electrodehydrating process, remove salt, water and tiny mechanical impurity;
5th step, by the blending ingredients distillation dehydration after electric desalting, its water ratio is made to be less than 0.05%;
Mixed reorganization after 6th step, the light oil the 3rd step distilled out dewater with the 5th step divides and mixes boiling bed hydrogenation device.
Example one
Coal tar is carried out centrifugation, twice filtration, mechanical impurity particle diameter is not more than 15 μm, coal tar is heated to 135 DEG C, injects the water accounting for coal tar gross weight 10%, adds and account for coal tar gross weight 50 μ g/g emulsion splitter; Metal remover 40 μ g/g, enters static mixer mixing, mixture strength 50KPa, and the de-tank electric field intensity inside high of electricity is 800V/cm, stops 40 minutes in electric field, and after three grades of electricity are de-, after tar character and hydrogenation, character sees the following form
Example two
Coal tar is carried out centrifugation, twice filtration, mechanical impurity particle diameter is not more than 15 μm, coal tar is heated to 130 DEG C, injects the water accounting for coal tar gross weight 8%, adds and account for coal tar gross weight 60 μ g/g emulsion splitter; Metal remover 70 μ g/g, enters static mixer mixing, mixture strength 60KPa, and the de-tank electric field intensity inside high of electricity is 100V/cm, stops 35 minutes in electric field, and after three grades of electricity are de-, after tar character and hydrogenation, character sees the following form
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.
Claims (4)
1. a coal tar deep processing pretreatment process, comprises the following steps:
The first step, centrifugation---be separated the solid impurity in coal tar by whizzer, make wherein contained solid grain size be less than 50 μm;
Second step, filtering separation---by the solid impurity in the further filtering separation coal tar of filtering material, make more than 15 μm wherein contained solids removal rates more than 98%;
3rd step, by the coal tar heating after centrifugal and filtering separation, distillation cuts out ammoniacal liquor, light oil, carbolic oil, ammoniacal liquor and carbolic oil is processed further, carbolic oil directly or after refining as industrial chemicals, by isolated light constituent, (density 20 DEG C, is not more than 0.98g/cm
3) mixing adds water, metal remover, emulsion splitter mix through static mixer; Remaining heavy constituent adds water, metal remover, emulsion splitter mix through static mixer;
4th step, by light constituent and heavy constituent mixed solution respectively through two-stage or three grades of electrodesalting and electrodehydrating process, remove salt, water and tiny mechanical impurity;
5th step, by the light constituent after electric desalting, heavy constituent respectively distillation dehydration, its water ratio is made to be less than 0.05%; Or make its water ratio be less than 0.05% light, heavy constituent mixing distillation dehydration;
6th step, hydrogenation unit is removed in light, the heavy constituent mixing after the 5th step dehydration.
2. a kind of coal tar deep processing pretreatment process according to claim 1, is characterized in that in described second step, and filter type is that gas back-flushing filters.
3. a kind of coal tar deep processing pretreatment process according to claim 1, is characterized in that in described 3rd step, distills the ammoniacal liquor obtained and is reclaimed by conventional acid wash, generate ammonium sulfate, and the phenols that carbolic oil obtains through conventional acid soda finishing is as industrial chemicals.
4. a kind of coal tar deep processing pretreatment process according to claim 1, is characterized in that isolated light constituent, heavy constituent carry out electrodesalting and electrodehydrating respectively; Light constituent electric desalting electric field is arranged in desalter middle and upper part, and oil-water mixture enters bottom electrical desalter; Heavy constituent electric desalting electric field arranges middle and lower part, and heavy constituent oil-water mixture enters from top.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367093A (en) * | 2016-10-18 | 2017-02-01 | 北京化工大学常州先进材料研究院 | Preparation method of low-ash mesophase pitch |
| CN106929082A (en) * | 2017-04-06 | 2017-07-07 | 上海蓝科石化环保科技股份有限公司 | A kind of coal tar preprocess method and system |
| CN109097085A (en) * | 2017-06-20 | 2018-12-28 | 中国石油化工股份有限公司 | The pretreated method of coal tar |
| CN110093184A (en) * | 2019-05-31 | 2019-08-06 | 武汉金中石化工程有限公司 | A kind of inferior heavy oil floating bed hydrogenation feed pretreatment technique |
| WO2020001206A1 (en) * | 2018-06-27 | 2020-01-02 | 河南龙成煤高效技术应用有限公司 | Method and apparatus for pre-treating low-temperature coal-tar before hydrogenation |
| CN110872530A (en) * | 2018-09-04 | 2020-03-10 | 武汉金中石化工程有限公司 | Coal tar pretreatment method and system |
| CN111154506A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Method for producing white oil by hydrogenation of coal tar |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106367093A (en) * | 2016-10-18 | 2017-02-01 | 北京化工大学常州先进材料研究院 | Preparation method of low-ash mesophase pitch |
| CN106929082A (en) * | 2017-04-06 | 2017-07-07 | 上海蓝科石化环保科技股份有限公司 | A kind of coal tar preprocess method and system |
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| CN109097085B (en) * | 2017-06-20 | 2021-11-16 | 中国石油化工股份有限公司 | Coal tar pretreatment method |
| WO2020001206A1 (en) * | 2018-06-27 | 2020-01-02 | 河南龙成煤高效技术应用有限公司 | Method and apparatus for pre-treating low-temperature coal-tar before hydrogenation |
| CN110872530A (en) * | 2018-09-04 | 2020-03-10 | 武汉金中石化工程有限公司 | Coal tar pretreatment method and system |
| CN111154506A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Method for producing white oil by hydrogenation of coal tar |
| CN110093184A (en) * | 2019-05-31 | 2019-08-06 | 武汉金中石化工程有限公司 | A kind of inferior heavy oil floating bed hydrogenation feed pretreatment technique |
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| CN105316018B (en) | 2017-12-19 |
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Address after: 212200 No. 2 CLP Road, Jiangsu, Yangzhong Patentee after: Samsung energy Polytron Technologies Inc Address before: 212200 No. 2, CLP Road, Yangzhong Development Zone, Jiangsu Patentee before: Changjiang (Yangzhong) Electric Desalting Equipment Co., Ltd. |