CN101629103A - Hydro-conversion combination method for coal tar fraction with different boiling ranges - Google Patents
Hydro-conversion combination method for coal tar fraction with different boiling ranges Download PDFInfo
- Publication number
- CN101629103A CN101629103A CN 200810170910 CN200810170910A CN101629103A CN 101629103 A CN101629103 A CN 101629103A CN 200810170910 CN200810170910 CN 200810170910 CN 200810170910 A CN200810170910 A CN 200810170910A CN 101629103 A CN101629103 A CN 101629103A
- Authority
- CN
- China
- Prior art keywords
- oil
- hydrogenation reaction
- hydrogenation
- high score
- fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a hydro-conversion combination method for a coal tar fraction with different boiling ranges, which comprises the following steps that: a first hydrogen fraction mainly comprising a coal tar light fraction is converted and separated at a first hydrogen device; a second hydrogen fraction mainly comprising a coal tar heavy fraction is converted and separated at a second hydrogen device; and two sets of the hydrogen devices share a circular hydrogen compressor; and the hydrogen light fraction obtained by the second hydrogen device enters a reaction part or a high fraction oil separating part of the first hydrogen device. The method can select respective proper hydrogen refining reaction conditions for the coal tar fraction with different boiling ranges, has the advantages of improving the quality of products, stabilizing the operation, reducing the energy consumption and catalyst consumption, prolong the operation cycle, simplifying the flow and the like, and is particularly suitable for large-scale classified combined hydro-conversion of medium-high temperature coal tar wide fractions.
Description
Technical field
The present invention relates to a kind of converting and combining method for hydrogenation of coal tar distillate with different boiling ranges, the extensive classification Unionfining that is particularly suitable for medium and high temperature coal tar wide fraction transforms.
Background technology
As everyone knows, original coal tar from pyrolysis of coal or coal generating gas or other process, contain the different boiling ranges fraction (such as the petroleum naphtha fraction if be suitable for the coal tar of hydrocracking, fraction of diesel oil, heavy fraction), then the character of different boiling ranges fraction is (such as hydrogen richness, density, viscosity, carbon residue content, metal content, oxygen level, sulphur content, nitrogen content, aromaticity content, burnt matter content, asphalt content, boiling point) difference is very big, when they are carried out hydrocracking production cleaning oil product, reaction mechanism, reaction pressure and temperature condition, the catalyzer configuration, the hydrogen consumption, the cycle of operation, fractionation mode and quality product are all inequality even difference is very big, for small-scale processing situation, relatively be suitable for uniting processing (the different boiling ranges fraction mixes and processes), can simplify flow process, reduce construction investment.But, unite processing and exist following shortcoming for the large-scale processing situation:
1. because impurity, metal, the carbon residue equal size difference of different boiling ranges fraction are big, to coal tar light fraction, coal tar heavy duty fraction blending fraction, take off in the reaction process of carbon residue agent at the agent of contact hydrogenation protecting, hydrodemetallation (HDM) agent, hydrogenation, the coal tar light fraction forms diluting effect to the coal tar heavy duty fraction, reduced reactant concn, increased hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogenation and taken off carbon residue agent consumption;
2. because easily reactant is as containing oxygen phenols, small molecules unsaturated hydrocarbons equal size than easy high many of the content of reactant in the coal tar heavy duty fraction in the coal tar light fraction, it is excessive to prevent beds local temperature rise that the coal tar light fraction need react at a lower temperature; But than under the low reaction temperatures, the coal tar heavy duty fraction is difficult to react, and the coal tar light fraction is formed diluting effect, has reduced reactant concn, has increased hydrogenation deoxidation agent consumption; For the high coal tar heavy duty fraction of viscosity, poor than the low reaction temperatures current downflow, it is excessive to cause the catalyst bed stressor layer to fall, and can't carry out the normal reaction operation;
3. because the size and the differences in shape of the mean molecule of petroleum naphtha fraction, fraction of diesel oil, heavy fraction are very big, the only catalyst formulation of said function (such as hydrodenitrification) is inevitable different, unites catalyzer and operational condition that processing can't be selected performance the best;
4. because the size and the differences in shape of the mean molecule of petroleum naphtha fraction, fraction of diesel oil, heavy fraction are very big, unite and add man-hour, as the hydrofining of whole realization appropriate depth, then must form excessive hydrogenation to a certain fraction, increase the hydrogen consumption, reduce liquid product yield;
5. because the coal tar hydrorefining process has " cracking " effect, heavy fraction unifining process " cracking " goes out petroleum naphtha fraction, fraction of diesel oil, but " cracking " goes out inconsistent than the time of small molecules, also there is the long weak point that has the unifining process time than small molecules, its refining effect is inconsistent, promptly select harsher hydrofining condition as guaranteeing the hydrofining effect that " cracking " goes out than small molecules, then other fraction is formed excessive hydrogenation, reduce liquid yield or reduce quality product, and increase hydrogen consumption and catalyzer consumption;
6. after different boiling ranges fraction mixed hydrogenation transforms, need between petroleum naphtha fraction, fraction of diesel oil, the heavy fraction distillation part from, it is huge to consume energy;
7. industry experience shows, petroleum naphtha fraction, fraction of diesel oil and heavy fraction are appointed the two mixing oil, in most cases there is certain demixing phenomenon in its storage tank, although employing jar interior pump circulation modes etc. are in the hope of homogenizing, but mixed coal tar character instability problem is difficult to thoroughly eliminate, this will cause full fraction or wide fraction coal tar hydrogenating unit feedstock property instability, hydrogenation reaction fluctuation of service, the fluctuation of service of the separate part of hydrogenation reaction effluent.
About the combined method of coal tar distillate with different boiling ranges difference hydrogenation, do not appear in the newspapers.
Obtain the also method of difference hydrogenation of coal tar distillate with different boiling ranges about separating original coal tar, do not appear in the newspapers.
The object of the present invention is to provide a kind of converting and combining method for hydrogenation of coal tar distillate with different boiling ranges.
Summary of the invention
The converting and combining method for hydrogenation of a kind of coal tar distillate with different boiling ranges of the present invention comprises the steps:
At first hydrogenation unit, in the first hydrogenation reaction part, mainly the first hydrocarbon fraction of being made up of the coal tar light fraction is finished first hydrogenation reaction and is converted into first hydrogenation reaction effluent, and first hydrogenation conditions is: temperature is that 200～460 ℃, pressure are that 4.0～30.0MPa, the first Hydrobon catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1; At the first high pressure separate part, separate first hydrogenation reaction effluent and obtain the first high score gas, first high score oil and the first high score water; In the separating of oil part of first high score, separate the first high score oil and obtain products such as first hydrogenated diesel oil; At least a portion first high score gas enters first hydrogenation reaction and partly does the use of first recycle hydrogen;
At second hydrogenation unit, in the second hydrogenation reaction part, main finish second hydrogenation reaction by the second hydrocarbon fraction of coal tar heavy duty fractional composition and be converted into second hydrogenation reaction effluent, second hydrogenation conditions is: temperature is that 220～480 ℃, pressure are that 4.0～30.0MPa, the second Hydrobon catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1; At the second high pressure separate part, separate second hydrogenation reaction effluent and obtain the second high score gas, second high score oil and the second high score water; In the separating of oil part of second high score, obtain products such as second hydrogenated diesel oil, the second hydrogenation heavy oil; At least a portion second high score gas enters second hydrogenation reaction and partly does the use of second recycle hydrogen;
First recycle hydrogen and the second recycle hydrogen common recycle hydrogen compressor.
Feature of the present invention further is:
In the separating of oil part of second high score, obtain the second hydrogenation light fraction oil, at least a portion second hydrogenation light fraction oil enters first hydrogenation reaction part and contacts with first Hydrobon catalyst.
Feature of the present invention further is:
In the separating of oil part of second high score, obtain low nitrogen content second hydrotreated naphtha and high nitrogen-containing second hydrotreated naphtha, at least a portion high nitrogen-containing second hydrotreated naphtha enters first hydrogenation reaction part and contacts with first Hydrobon catalyst.
Feature of the present invention further is:
In the separating of oil part of second high score, enter second light pressure separator after the oil decompression of second high score and be separated into second low pressure gas and the second low oil that divides, second low divide oil enter second low divide oily separation column to be separated into second low to divide oil content to heat up in a steamer column overhead gas, heavy hydrocarbons be that second of hydrogenated diesel oil fraction lowly divides oil content to heat up in a steamer column overhead oil and the second low oil content that divides heats up in a steamer oil at the bottom of the Tata; At least a portion second low branch oil content heats up in a steamer column overhead oil and enters the separating of oil part of first high score.
Feature of the present invention further is:
Heavy hydrocarbons is the hydrogenated diesel oil fraction in the first high score oil.
Feature of the present invention further is:
First hydrogenation conditions is: temperature is that 200～430 ℃, pressure are that 6.0～25.0MPa, the first Hydrobon catalyst volume space velocity are 0.05～4.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1;
Second hydrogenation conditions is: temperature is that 240～430 ℃, pressure are that 6.0～25.0MPa, the second Hydrobon catalyst volume space velocity are 0.05～4.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
Feature of the present invention further is:
The nitrogen content of hydrotreated naphtha (mean value) is lower than 10PPm;
The cetane value of hydrogenated diesel oil (mean value) is higher than 30.
Feature of the present invention further is:
The nitrogen content of hydrotreated naphtha (mean value) is lower than 4PPm;
The cetane value of hydrogenated diesel oil (mean value) is higher than 35.
Feature of the present invention further is:
At the coal tar separate part, separate original coal tar and obtain the first hydrocarbon fraction and the second hydrocarbon fraction, the first hydrocarbon fraction and the second hydrocarbon fraction go first hydrogenation reaction part and the second hydrogenation reaction part respectively.
Feature of the present invention further is:
At the coal tar separate part, separate original coal tar and obtain the first hydrocarbon fraction, second hydrocarbon fraction and the coal-tar pitch, the first hydrocarbon fraction and the second hydrocarbon fraction go first hydrogenation reaction part and the second hydrogenation reaction part respectively.
Feature of the present invention further is:
In the 3rd hydrogenation reaction part, the second hydrogenation heavy oil is finished the 3rd hydrogenation reaction and is converted into the 3rd hydrogenation reaction effluent, and the 3rd hydrogenation conditions is: temperature is that 280～480 ℃, pressure are that 4.0～30.0MPa, the 3rd hydrocracking catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1.
Feature of the present invention further is:
The 3rd hydrogenation conditions is: temperature is that 350～460 ℃, pressure are that 6.0～25.0MPa, the 3rd hydrocracking catalyst volume space velocity are 0.1～2.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
Feature of the present invention further is:
At the 3rd high pressure separate part, separate the 3rd hydrogenation reaction effluent and obtain the 3rd high score gas, the 3rd high score oil;
At least a portion the 3rd high score gas enters the 3rd hydrogenation reaction and partly does the use of the 3rd recycle hydrogen;
First recycle hydrogen, second recycle hydrogen and the 3rd recycle hydrogen common recycle hydrogen compressor.
In the separating of oil part of the 3rd high score, obtain products such as the 3rd hydrogenated diesel oil.
Feature of the present invention further is:
In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenation heavy oil, at least a portion the 3rd hydrogenation heavy oil goes second hydrogenation reaction part to contact with second Hydrobon catalyst.
Feature of the present invention further is:
In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenation heavy oil, at least a portion the 3rd hydrogenation heavy oil goes the 3rd hydrogenation reaction part to contact with the 3rd hydrocracking catalyst.
Feature of the present invention further is:
The 3rd hydrogenation reaction effluent enters the separating of oil part of second high score.
Feature of the present invention further is:
The 3rd hydrogenation reaction effluent enters second hydrogenation reaction part and contacts with second Hydrobon catalyst.
Feature of the present invention further is:
The beds inlet that the 3rd hydrogenation reaction effluent enters behind second hydrogenation reaction catalyst for demetalation bed partly contacts with described beds.
Embodiment
Below describe the present invention in detail.
Conventional boiling point of the present invention refers to vapour, the liquid equilibrium temperature of material under a barometric point.Conventional liq hydrocarbon of the present invention refers to the hydro carbons that is in a liquid state under the normal condition, comprises the hydro carbons that pentane and boiling point thereof are higher.Proportion of the present invention unless stated otherwise, refers to the ratio of water-mass density under fluid density and normal pressure under normal pressure, the 15.6 ℃ of conditions, the 15.6 ℃ of conditions.The composition of component of the present invention or concentration or content value unless stated otherwise, are the weight basis value.
It is the coal tar hydro carbons that is suitable for doing the petroleum naphtha fraction that the latent fraction of coal-tar naphtha of the present invention refers to hydrocracking, and its conventional boiling point is generally 60～190 ℃, is generally 60～180 ℃.
It is the coal tar hydro carbons that is suitable for doing fraction of diesel oil that the latent fraction of coal tar diesel oil of the present invention refers to hydrocracking, and its conventional boiling point is generally 160～390 ℃, is generally 180～370 ℃.
Coal tar light fraction of the present invention refer to coal-tar naphtha dive fraction and or the coal tar diesel oil fraction of diving, its conventional boiling point is generally 60～390 ℃, is generally 60～370 ℃.
Coal tar heavy oil fraction of the present invention refer to conventional boiling point generally be higher than 370 ℃, usually above 390 ℃ fractions.
The coal tar that contains heavy fraction of the present invention, the content of its heavy fraction generally is higher than 10%, usually above 30%, preferably be higher than 40%.
Wide fraction coal tar of the present invention refers to the coal tar that contains coal tar light fraction and coal tar heavy duty fraction, and its conventional boiling point is generally 60～550 ℃.
The conventional boiling spread of the fraction that is suitable for hydrogenation of most coal-tar middle oils is generally 100～530 ℃.
Coal tar of the present invention refers to the coal-tar products from pyrolysis of coal or coal generating gas or other process that is suitable for hydro-upgrading, normally from the fraction lighter than coal-tar pitch component of coal-tar products.Therefore, can be the fraction (being lower than 450 ℃ of fractional compositions) of the by product (coalite tar) of coal generating gas, also can be the coal coking pyrolysis of coal process by product coal tar or the coal tar distillate of (comprising semi-coking, middle coking, high-temperature coking process) by conventional boiling temperature, its conventional boiling temperature is usually less than 530 ℃, and coal tar of the present invention can also be the mixing oil of above-mentioned coal tar.Because naphthalene price height (about 7000 yuan/ton) for the coal-tar heavy oil fraction, enters before the hydro-upgrading unit, incited somebody to action naphthalene Separation and Recovery wherein usually.
Because raw coal character and coking or gas-making process condition all change within the specific limits, the coal tar oil properties also changes within the specific limits.Coal tar oil properties proportion of the present invention is generally 0.89～1.25, and conventional boiling point is generally 60～530 ℃ and is generally 120～510 ℃, and usually metal content is that 5～80PPm, sulphur content are 0.1～0.4%, nitrogen content is 0.6～1.6%.Coal tar of the present invention, inorganic sometimes water-content is 0.2～5.0%, organic sometimes oxygen level is 2.5～11%, especially be 3.5～10%, be 5～10% more particularly.
According to the present invention, described coal tar carries out before the hydrogenation, the common process of passing through dehydration and crossing the filtering solid particulate.
The first hydrocarbon fraction of the present invention refers to the hydrocarbon fraction of mainly being made up of the coal tar light fraction, it can be the coalite tar light fraction from the tank field, also can be the fraction that initial coalite tar separate part obtains, can also be the fraction that initial coal-tar middle oil or coal-tar heavy oil separate part obtain.
The second hydrocarbon fraction of the present invention refers to main hydrocarbon fraction by coal tar heavy duty fractional composition, it can be the coalite tar heavy fraction from the tank field, also can be the fraction that initial coalite tar separate part obtains, can also be the fraction that initial coal-tar middle oil or coal-tar heavy oil separate part obtain.
Coal tar heavy oil contains the coal tar coal-tar pitch that is not suitable for hydrotreatment sometimes, and also can obtain coal-tar pitch product at the separate part of the original coal tar that contains coalite tar heavy oil this moment.
Coal tar separate part of the present invention, its whole raw materials contain coal tar light fraction and coal tar heavy duty fraction at least, also may contain the coal-tar pitch component.
Coal tar separate part of the present invention, its product have the first hydrocarbon fraction and the main second hydrocarbon fraction of mainly being made up of the coal tar light fraction by coal tar heavy duty fractional composition at least, also have coal-tar pitch.
Coal tar separate part of the present invention adopts underpressure distillation part to operate from mode usually, and its underpressure distillation column overhead working pressure (absolute pressure) generally is lower than 0.06MPa, is usually less than 0.04MPa.
Converting and combining method for hydrogenation according to a kind of coal tar distillate with different boiling ranges of the present invention comprises the steps:
At first hydrogenation unit, in the first hydrogenation reaction part, mainly the first hydrocarbon fraction of being made up of the coal tar light fraction is finished first hydrogenation reaction and is converted into first hydrogenation reaction effluent, and first hydrogenation conditions is: temperature is that 200～460 ℃, pressure are that 4.0～30.0MPa, the first Hydrobon catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1; At the first high pressure separate part, separate first hydrogenation reaction effluent and obtain the first high score gas, first high score oil and the first high score water; In the separating of oil part of first high score, separate the first high score oil and obtain products such as first hydrogenated diesel oil; At least a portion first high score gas enters first hydrogenation reaction and partly does the use of first recycle hydrogen;
At second hydrogenation unit, in the second hydrogenation reaction part, main finish second hydrogenation reaction by the second hydrocarbon fraction of coal tar heavy duty fractional composition and be converted into second hydrogenation reaction effluent, second hydrogenation conditions is: temperature is that 220～480 ℃, pressure are that 4.0～30.0MPa, the second Hydrobon catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1; At the second high pressure separate part, separate second hydrogenation reaction effluent and obtain the second high score gas, second high score oil and the second high score water; In the separating of oil part of second high score, obtain products such as second hydrogenated diesel oil, the second hydrogenation heavy oil; At least a portion second high score gas enters second hydrogenation reaction and partly does the use of second recycle hydrogen;
First recycle hydrogen and the second recycle hydrogen common recycle hydrogen compressor.
In order further to improve the second hydrogenation light fraction oil quality:
In the separating of oil part of second high score, obtain the second hydrogenation light fraction oil, at least a portion second hydrogenation light fraction oil enters first hydrogenation reaction part and contacts with first Hydrobon catalyst.
In order further to reduce by the second hydrotreated naphtha nitrogen content:
In the separating of oil part of second high score, obtain low nitrogen content second hydrotreated naphtha and high nitrogen-containing second hydrotreated naphtha, at least a portion high nitrogen-containing second hydrotreated naphtha enters first hydrogenation reaction part and contacts with first Hydrobon catalyst.
In order to simplify the second high score oil separation part branch flow process:
In the separating of oil part of second high score, enter second light pressure separator after the oil decompression of second high score and be separated into second low pressure gas and the second low oil that divides, second low divide oil enter second low divide oily separation column to be separated into second low to divide oil content to heat up in a steamer column overhead gas, heavy hydrocarbons be that second of hydrogenated diesel oil fraction lowly divides oil content to heat up in a steamer column overhead oil and the second low oil content that divides heats up in a steamer oil at the bottom of the Tata; At least a portion second low branch oil content heats up in a steamer column overhead oil and enters the separating of oil part of first high score.
In order to simplify the first high score oil separation part branch flow process: heavy hydrocarbons is preferably the hydrogenated diesel oil fraction in the first high score oil.
The first suitable hydrogenation conditions is: temperature is that 200～430 ℃, pressure are that 6.0～25.0MPa, the first Hydrobon catalyst volume space velocity are 0.05～4.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
The second suitable hydrogenation conditions is: temperature is that 240～430 ℃, pressure are that 6.0～25.0MPa, the second Hydrobon catalyst volume space velocity are 0.05～4.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
Quality product target of the present invention: the nitrogen content of hydrotreated naphtha (mean value) generally is lower than 10PPm, is preferably lower than 4PPm; The cetane value of hydrogenated diesel oil (mean value) is higher than 30, preferably is higher than 35.
For the further cracking second hydrogenation heavy oil:
In the 3rd hydrogenation reaction part, the second hydrogenation heavy oil is finished the 3rd hydrogenation reaction and is converted into the 3rd hydrogenation reaction effluent, and the 3rd hydrogenation conditions is: temperature is that 280～480 ℃, pressure are that 4.0～30.0MPa, the 3rd hydrocracking catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1.
The 3rd suitable hydrogenation conditions is: temperature is that 350～460 ℃, pressure are that 6.0～25.0MPa, the 3rd hydrocracking catalyst volume space velocity are 0.1～2.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
In order to simplify flow process: first recycle hydrogen, second recycle hydrogen and the 3rd recycle hydrogen common recycle hydrogen compressor.
In order to make with extra care the 3rd hydrogenation heavy oil:
In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenation heavy oil, at least a portion the 3rd hydrogenation heavy oil goes second hydrogenation reaction part to contact with second Hydrobon catalyst.
For cracking the 3rd hydrogenation heavy oil:
In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenation heavy oil, at least a portion the 3rd hydrogenation heavy oil goes the 3rd hydrogenation reaction part to contact with the 3rd hydrocracking catalyst.
In order to simplify the 3rd high score oil separation part branch flow process:
The 3rd hydrogenation reaction effluent enters the separating of oil part of second high score.
In order to utilize the 3rd hydrogenation reaction effluent to increase the second hydrogenation reaction portion of hot capacity, reduce by the second hydrogenation reaction part temperature rise, stable operation: the 3rd hydrogenation reaction effluent is entered second hydrogenation reaction part contact with second Hydrobon catalyst.
In order to reduce system pressure drop, shorten go into operation, shut-down, accident treatment time: the beds inlet that the 3rd hydrogenation reaction effluent is incorporated into behind the catalyst for demetalation bed of second hydrogenation reaction part contacts with described beds.
In the first hydrogenation reaction part, under the first Hydrobon catalyst existence condition, the described first hydrocarbon fraction is finished first hydrogenation reaction, generates first hydrogenation reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.
First hydrogenation reaction of the present invention, be commonly referred to as the reaction process of the consumption hydrogen that the first hydrocarbon fraction takes place under the hydrogen and the suitable first Hydrobon catalyst existence condition, its minimum reaction depth should possess MIN industrial significance: promptly the first hydrocarbon fraction is finished the hydrofining of expection, the nitrogen content (mean value) of hydrotreated naphtha that this process is won is lower than 10PPm, should be lower than 4PPm, be preferably lower than 2PPm, to be suitable for doing petroleum naphtha catalytic reforming raw material blend component; The cetane value (mean value) of hydrogenated diesel oil that this process is won generally is higher than 30, usually above 35.The first hydrogenation reaction degree of depth should determine that generally this process is reduced to the nitrogen content of first hydrogenated diesel oil below the 800PPm, preferably is reduced to below the 400PPm according to the first hydrocarbon fraction character; General this process is reduced to the sulphur content of first hydrogenated diesel oil below the 400PPm, is reduced to usually below the 300PPm, preferably is reduced to below the 200PPm; General this process to the carbon residue decreasing ratio of the first hydrocarbon fraction greater than 70%, usually greater than 90%, more preferably greater than 95%.
The described first hydrogenation reaction part, different because of difference and the first hydrogenation reaction degree of depth of the first hydrocarbon fraction character (metal content, oxygen level content, olefin(e) centent, sulphur content, nitrogen content, aromaticity content, boiling range, proportion) (hydrogenation deoxidation, hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated), the variation range of its operational condition is very wide, should determine according to concrete process condition.
The described first hydrogenation reaction part, first Hydrobon catalyst of use can be the series combinations of one or both or multiple catalyzer and load in mixture.First Hydrobon catalyst, can be coal tar light fraction hydrofining special-purpose catalyst, also can be Hydrobon catalyst and combination thereof with functions such as hydrodemetallation (HDM) or hydrogenation deoxidation or hydrogenating desulfurization or hydrodenitrification or hydrogenation are saturated that the unifining process of suitable refining of petroleum gasoline or diesel oil or wax oil uses.
Described first hydrogenation unit, any additional sulphur can be added the first hydrogenation reaction part as required, with guarantee the necessary minimum concentration of hydrogen sulfide of reactive moieties such as 500PPm (v) or 1000PPm (v), to guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value.Described additional sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide the coal tar hydrogenating conversion process is not had the material of undesirable action, such as hydrogen sulfide containing gas or oil product, or contact the back with high-temperature hydrogen and generate the dithiocarbonic anhydride of hydrogen sulfide or Methyl disulfide etc.
At the first high pressure separate part, separate first hydrogenation reaction effluent and obtain the first high score gas, first high score oil and the first high score water; In the separating of oil part of first high score, obtain products such as first hydrogenated diesel oil; At least a portion first high score gas enters first hydrogenation reaction and partly does the use of first recycle hydrogen.
First hydrogenation reaction effluent enters before the first high pressure separate part, injects washing water usually in first hydrogenation reaction effluent.Described first hydrogenation reaction effluent usually earlier reduces temperature (generally being and reactive moieties charging heat exchange), mixes first hydrogenation reaction effluent after the formation water filling then with the washing water that add.Washing water are used for absorbing ammonia and issuable other impurity such as the hydrogenchloride etc. of first hydrogenation reaction effluent, and the aqueous solution behind the absorption ammonia must absorb the hydrogen sulfide in first hydrogenation reaction effluent.
The described first high pressure separate part comprises cooling, the separating step of first hydrogenation reaction effluent after the water filling.At this, first hydrogenation reaction effluent reduces temperature (using air-cooler and or watercooler usually) earlier usually to about 30～70 ℃ after the described water filling.
At the first high pressure separate part, first hydrogenation reaction effluent is separated into after the described water filling: first a high score gas of mainly being made up of hydrogen on volume, the first high score oil, main first a high score water that be made up of water and that be dissolved with hydrogen sulfide, ammonia of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.The described first high score water, wherein the content of ammonia is generally 1～15% (w), is preferably 3～8% (w).A purpose annotating washing water is ammonia and the hydrogen sulfide that absorbs in first hydrogenation reaction effluent, prevents that first hydrogenation reaction effluent process that cools from forming sulphur hydrogenation ammonia or heat exchanger channel is stopped up in the crystallization of many sulphur ammonia, increases system pressure drop.
The injection rate of described washing water, should determine according to following principle: on the one hand, washing water are divided into vapour phase water and liquid phase water after injecting first hydrogenation reaction effluent, the liquid phase water yield must be greater than zero, be preferably the washing water total amount 30% or more; On the one hand, washing water are used for absorbing the ammonia of first hydrogenation reaction effluent, prevent that the ammonia concentration of the first high score gas is too high again, reduce catalyst activity, the ammonia volumetric concentration of the common first high score gas is low more good more, generally is not more than 200PPm and (v), preferably is not more than 50PPm (v).
The described first high pressure separate part, its separator operation pressure are that the first hydrogenation reaction partial pressure deducts true pressure and falls, and the difference of the first high pressure separate part working pressure and the first hydrogenation reaction pressure should not be crossed lowly or too high, is generally 0.5～1.2MPa.
The described first high score gas, its density of hydrogen value, should not be low excessively (causing the device working pressure to rise), generally should be not less than 70% and (v), should be not less than 80% and (v), preferably be not less than 85% (v).
As previously mentioned at least a portion, be generally 85～100% the first high score gas and return first hydrogenation reaction and partly form first recycle hydrogen, to provide the first hydrogenation reaction part necessary amounts of hydrogen and hydrogen concentration; In order to improve plant investment efficient, must guarantee that recycle hydrogen concentration is not less than aforesaid low limit value,, distribute for this reason, can get rid of the described first high score gas of a part (hereinafter to be referred as the first discharging gas) to get rid of methane, the ethane that reaction produces according to concrete feedstock property, reaction conditions, product.For the first discharging gas, can adopt conventional membrane separation process or pressure swing adsorption technique or oil wash technology to realize that hydrogen separates with non-hydrogen gaseous fraction, and the hydrogen that reclaims is used as new hydrogen.
Before the first high pressure separate part the first thermal high separate part can be set.
The separating of oil part of first high score described herein is meant the step that the first high score fluid body is separated into product, and its liquid product comprises mainly by conventional boiling point and is higher than the hydrocarbon ils that 50 ℃ petroleum naphtha component is formed, and heavy hydrocarbons is a fraction of diesel oil in the best first high score oil.At this, the described first high score oil at first reduces pressure, pressure is reduced to 0.5～4.0MPa formation gas, the logistics of liquid mixed phase usually, then through separation with or fractionated process finish and separate, be separated into gas, liquefied gas, first hydrotreated naphtha, first hydrogenated diesel oil etc. usually.
In the second hydrogenation reaction part, under the second Hydrobon catalyst existence condition, described second hydrocarbon fraction and hydrogen are finished second hydrogenation reaction, generate second hydrogenation reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.
Second hydrogenation reaction of the present invention, be commonly referred to as the refining reaction process of the consumption hydrogen that the second hydrocarbon fraction takes place under hydrogen and appropriate catalyst existence condition, its minimum reaction depth should possess MIN industrial significance: promptly the second hydrocarbon fraction is finished the hydrofining of expection, the nitrogen content (mean value) of this process gained second hydrotreated naphtha is lower than 10PPm, should be lower than 4PPm, be preferably lower than 2PPm, to be suitable for doing petroleum naphtha catalytic reforming raw material blend component; The cetane value (mean value) of this process gained second hydrogenated diesel oil generally is higher than 30, usually above 35.
Second hydrogenation reaction of the present invention, be commonly referred to as the refining reaction process of the consumption hydrogen that the second hydrocarbon fraction takes place under hydrogen and appropriate catalyst existence condition, its minimum reaction depth should possess MIN industrial significance: be the 3rd hydrogenation reaction part (being generally the hydrocracking part) proper raw material oil is provided, should determine the requirement of feedstock property according to the second hydrocarbon fraction character and the 3rd hydrogenation reaction part catalyzer: generally this process is reduced to the living olefiant nitrogen content of second hydrogenation reaction below the 1500PPm, usually be reduced to below the 800PPm, preferably be reduced to below the 400PPm; General this process is given birth to olefiant sulphur content with second hydrogenation reaction and is reduced to below the 400PPm, is reduced to usually below the 300PPm, preferably is reduced to below the 200PPm; General this process to the carbon residue decreasing ratio of feed coal tar greater than 70%, usually greater than 90%, more preferably greater than 95%, to delay the knot charcoal speed of the 3rd hydrogenation reaction partial hydrogenation catalyzer, prolong the operational cycle of the 3rd hydrogenation reaction part catalyzer.
The described second hydrogenation reaction part, different because of the difference of the second hydrocarbon fraction character (metal content, oxygen level, sulphur content, nitrogen content, aromaticity content, boiling range, proportion) and the second hydrogenation reaction degree of depth (hydrogenation deoxidation, hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated), the variation range of its operational condition is very wide, should determine according to concrete process condition.
The described second hydrogenation reaction part, second Hydrobon catalyst of use comprises Hydrobon catalyst usually, and described Hydrobon catalyst can be the series combination of one or both or multiple catalyzer and load in mixture.Hydrobon catalyst can be suitable refining of petroleum diesel oil and/or wax oil/or Hydrobon catalyst and combinations thereof such as the hydrogenating desulfurization agent used of the unifining process of heavy oil, hydrodenitrification agent, removal of ccr by hydrotreating, hydrogenation aromatic hydrocarbons saturator.Because the second hydrocarbon fraction metal content is higher usually, so use Hydrodemetalation catalyst before Hydrobon catalyst.
The described second hydrogenation reaction part, any additional sulphur can be added reactive moieties as required, with guarantee the necessary minimum concentration of hydrogen sulfide of reactive moieties such as 500PPm (v) or 1000PPm (v), to guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value.Described additional sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide the coal tar hydrogenating conversion process is not had the material of undesirable action, such as hydrogen sulfide containing gas or oil product, or with the dithiocarbonic anhydride that is converted into hydrogen sulfide after high-temperature hydrogen contacts or Methyl disulfide etc.
At the second high pressure separate part, separate second hydrogenation reaction effluent and obtain the second high score gas, second high score oil and the second high score water; In the separating of oil part of second high score, obtain products such as second hydrogenated diesel oil; At least a portion second high score gas enters second hydrogenation reaction and partly does the use of second recycle hydrogen.
The water filling principle of second hydrogenation reaction effluent, the second high pressure separate part operating principle, the second high score gas circle principle are analogous to water filling principle, the first high pressure separate part operating principle, the first high score gas circle principle of first hydrogenation reaction effluent substantially.
Before the second high pressure separate part the second thermal high separate part can be set.
The separating of oil part of second high score described herein is meant the step that the second high score fluid body is separated into product, and its liquid product comprises products such as second hydrotreated naphtha, second hydrogenated diesel oil, the second hydrogenation heavy oil usually.At this, the described second high score oil at first reduces pressure, pressure is reduced to 0.5～4.0MPa formation gas, the logistics of liquid mixed phase usually, then through separation with or fractionated process finish and separate, be separated into gas, liquefied gas, second hydrotreated naphtha, second hydrogenated diesel oil, the second hydrogenation heavy oil etc. usually.
Below describe the 3rd hydrogenation reaction part of the present invention in detail.
In the 3rd hydrogenation reaction part, under the 3rd hydrocracking catalyst existence condition, described second hydrogenation heavy oil of at least a portion and hydrogen are finished the 3rd hydrogenation reaction, generate the 3rd hydrogenation reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.
Described the 3rd hydrogenation reaction part, different because of the 3rd hydrogenation reaction degree of depth of the difference of its raw material (the second hydrogenation heavy fraction) character (nitrogen content, aromaticity content) and expection, the variation range of its operational condition is very wide, should determine according to concrete process condition.
The 3rd hydrogenation reaction part as mentioned above, the hydrocracking catalyst of use can be the series combinations of one or both or multiple catalyzer and load in mixture.Hydrocracking catalyst can be suitable petroleum refining process diesel oil (comprising poor ignition quality fuel) and/or wax oil/or the hydrocracking process of heavy oil hydrocracking catalyst (comprise and relax cracking catalyst) and combination thereof of using.
The 3rd hydrogenation reaction part as mentioned above, can select amorphous (sial) hydrocracking catalyst of not fusion molecular sieve or amorphous (sial) hydrocracking catalyst of a small amount of fusion molecular sieve for use, to strengthen adaptive faculty as far as possible, improve the diesel component productive rate to organic nitrogen compound in the raw material.Second hydrogenation reaction part also can use Hydrobon catalyst and hydrocracking catalyst and back catalyst for refining to carry out grating.
The 3rd hydrogenation reaction one speech of the 3rd hydrogenation reaction part of the present invention, refer under hydrogen and appropriate catalyst existence condition, the reaction process (comprising cracking reaction usually) of the consumption hydrogen that the 3rd hydrogenation reaction part material fry dried food ingredients is given birth to, its minimum reaction depth should possess MIN industrial significance: such as the fraction of diesel oil of producing expection character, should be according to the 3rd hydrogenation reaction part material oil nature, expection fraction of diesel oil character and the 3rd hydrogenation catalyst performance are determined: in the hope of improving the fraction of diesel oil cetane value, reduce fraction of diesel oil density to re-set target, take into account liquid yield simultaneously, this process cracking conversion rate is generally 30～80%, be generally 45～65%.
According to the present invention, the Separation and Recovery scheme of the 3rd hydrogenation reaction effluent has multiple.
The Separation and Recovery scheme of first kind of the 3rd hydrogenation reaction effluent is that the independently Separation and Recovery process of the 3rd hydrogenation reaction effluent is set.At the 3rd high pressure separate part, separate the 3rd hydrogenation reaction effluent and obtain the 3rd high score gas and the 3rd high score oil; In the separating of oil part of the 3rd high score, obtain products such as the 3rd hydrogenated diesel oil; At least a portion the 3rd high score gas enters the 3rd hydrogenation reaction and partly does the use of the 3rd recycle hydrogen.The water filling principle of the 3rd hydrogenation reaction effluent, the 3rd high pressure separate part operating principle, the 3rd high score circle principle are analogous to water filling principle, the first high pressure separate part operating principle, the first high score gas circle principle of first hydrogenation reaction effluent substantially.In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenated diesel oil and possible products such as the 3rd hydrogenation heavy oil; Part or all of the 3rd hydrogenation heavy oil can return the 3rd hydrogenation reaction part or the second hydrogenation reaction part.
The Separation and Recovery scheme of second kind of the 3rd hydrogenation reaction effluent, be that the 3rd hydrogenation reaction effluent is incorporated into the second high pressure separate part and the recovery of the second hydrogenation reaction effluent combined separation, to simplify flow process, common the 3rd hydrogenation reaction effluent mixes the back and introduces the second high pressure separate part with second hydrogenation reaction effluent.The part or all of second hydrogenation heavy oil circulation component part circulation or the cracking flow process that all circulates.
The Separation and Recovery scheme of the third the 3rd hydrogenation reaction effluent, be that arbitrary beds inlet that the 3rd hydrogenation reaction effluent is incorporated into second hydrogenation reaction part contact with described beds, recommend that the 3rd hydrogenation reaction effluent is incorporated into beds behind second hydrogenation reaction catalyst for demetalation bed partly and enter the mouth and contact with described beds.The part or all of second hydrogenation heavy oil circulation component part circulation or the cracking flow process that all circulates.
Metal, oxygen, sulphur, the nitrogen of the typical coal tar hydrogenating conversion process of the present invention in can effective elimination coal tar, make wherein saturated, the cracking of at least a portion polynuclear compound, oil property is improved significantly, and petroleum naphtha fraction product can be used as high-quality catalytic reforming raw material component, the fraction of diesel oil product can be used as fine-quality diesel oil blending component.
New hydrogen enters and adds hydrogen partial to replenish the hydrogen that adds hydrogen partial consumption, and new hydrogen hydrogen concentration is high more good more, generally should not be lower than 95% and (v), preferably be not less than 99% (v).
In order to implement the present invention, all new hydrogen can be introduced first hydrogenation reaction part or second hydrogenation reaction part or the 3rd hydrogenation reaction part.
The invention has the advantages that:
1. to the fraction of different boiling ranges, select suitable separately hydrofining reaction condition, can improve the quality of products, quiet run, raising liquid product yield, reduce catalyst levels, avoid excessive hydrogen consumption, save and separate power consumption, so the extensive classification Unionfining that the present invention is suitable for wide fraction coal tar transforms;
2. recycle hydrogen common recycle hydrogen compressor can be simplified flow process;
3. the second hydrogenation light fraction is introduced the first hydrogenation reaction part, to its further hydrofining, can improve its quality with simple process flow, appropriate condition;
4. the 3rd hydrogenation reaction effluent is incorporated into the second high pressure separate part and the 3rd hydrogenation reaction effluent combined separation and reclaims, to simplify flow process.The part or all of second hydrogenation heavy oil circulation component part circulation or the cracking flow process that all circulates.
5. the arbitrary beds inlet that the 3rd hydrogenation reaction effluent is incorporated into second hydrogenation reaction part contact with described beds, recommends that the 3rd hydrogenation reaction effluent is incorporated into beds behind second hydrogenation reaction catalyst for demetalation bed partly and enters the mouth and contact with described beds.The part or all of second hydrogenation heavy oil circulation component part circulation or the cracking flow process that all circulates.
6. to the first hydrocarbon fraction and the charging respectively of the second hydrocarbon fraction of different boiling ranges, stablized hydrogenating materials character.
Embodiment one
Coal-tar middle oil character sees Table 1, finishing one-level after being warming up to 80 ℃ filters, finish cascade filtration after further being warming up to 170 ℃, one-level vacuum flashing dehydration, after further heating up, one-level dehydration back coal-tar middle oil finishes underpressure distillation part from (finishing the secondary dehydration simultaneously) under condition of negative pressure, if separation column charging process furnace, fractionator overhead pressure is～0.03MPa (absolute pressure), the separation column hypomere is the water vapor stripping stage, the separation column epimere is a rectifying section, and all coal tar is separated into the overhead oil (conventional boiling point is lower than 250 ℃) that return tank of top of the tower is discharged, midsection is extracted the coal tar heavy duty fraction of discharging at the bottom of oil (250～330 ℃ of conventional boiling points) and the tower out.Overhead oil and stage casing are extracted the oil mixing out as the first hydrocarbon fraction, and the coal tar heavy duty fraction is as the second hydrocarbon fraction.
According to the present invention, at first hydrogenation unit, in the first hydrogenation reaction part, the first hydrocarbon fraction is converted into first hydrogenation reaction effluent, and heavy hydrocarbons is the first hydrogenated diesel oil fraction in first hydrogenation reaction effluent.
At the first high pressure separate part, separate first hydrogenation reaction effluent and obtain the first high score gas, first high score oil and the first high score water; In the separating of oil part of first high score, obtain products such as first hydrotreated naphtha, first hydrogenated diesel oil; The first high score gas enters first hydrogenation reaction and partly does the use of first recycle hydrogen.
At second hydrogenation unit, in the second hydrogenation reaction part, the second hydrocarbon fraction is converted into second hydrogenation reaction effluent; At the second high pressure separate part, separate second hydrogenation reaction effluent and obtain the second high score gas, second high score oil and the second high score water; The second high score gas enters second hydrogenation reaction and partly does the use of second recycle hydrogen.In the separating of oil part of second high score, enter second light pressure separator after the oil decompression of second high score and be separated into second low pressure gas and the second low oil that divides, second low divide oil enter second low divide oily separation column to be separated into second low to divide oil content to heat up in a steamer column overhead gas, heavy hydrocarbons be that second of hydrogenated diesel oil fraction lowly divides oil content to heat up in a steamer column overhead oil and the second low oil content that divides heats up in a steamer oil at the bottom of the Tata; The second low branch oil content heats up in a steamer column overhead oil and enters the separating of oil part of first high score.
Oil further was separated into second hydrogenated diesel oil, the second hydrogenation heavy oil at the bottom of the second low branch oil content heated up in a steamer Tata, and whole second hydrogenation heavy oil partly are converted into the 3rd hydrogenation reaction effluent in the 3rd hydrogenation reaction.
The Separation and Recovery scheme of the 3rd hydrogenation reaction effluent is that the independently Separation and Recovery process of the 3rd hydrogenation reaction effluent is set.At the 3rd high pressure separate part, separate the 3rd hydrogenation reaction effluent and obtain the 3rd high score gas, the 3rd high score oil and the 3rd high score water; At least a portion the 3rd high score gas enters the 3rd hydrogenation reaction and partly does the use of the 3rd recycle hydrogen.The water filling principle of the 3rd hydrogenation reaction effluent, the 3rd high pressure separate part operating principle, the 3rd high score circle principle are analogous to water filling principle, the first high pressure separate part operating principle, the first high score gas circle principle of first hydrogenation reaction effluent substantially.In the separating of oil part of the 3rd high score, obtain products such as the 3rd hydrogenated diesel oil and the 3rd hydrogenation heavy oil; Whole the 3rd hydrogenation heavy oil return the 3rd hydrogenation reaction part.
Recycle hydrogen common recycle hydrogen compressor.
Coal tar character sees Table 1, the hydrogenation catalyst composition sees Table 2, operational condition and product property see Table 3, and technical solution of the present invention has realized the production purpose: the cetane value (mean value) that the nitrogen content of the first hydrotreated naphtha fraction (mean value) is lower than 3PPm, the second hydrogenated diesel oil fraction is higher than 33.
The advantage of embodiment is:
1. the first hydrogenation reaction part of the first hydrocarbon fraction is used metal remover, hydrogenation deoxidation agent and hydrofining agent; The second hydrogenation reaction part of the second hydrocarbon fraction is used protective material, metal remover, is taken off carbon residue agent and hydrofining agent (be different from first hydrogenation reaction and partly use the hydrofining agent);
2. first hydrogenation reaction part is partly compared with second hydrogenation reaction, initial reaction temperature differs from 50 ℃, selected suitable reaction temperature separately for use, avoid the fraction of diesel oil excessive hydrogenation, reduced the hydrogen consumption, increased liquid product yield, the cetane value (mean value) that the nitrogen content (mean value) that has guaranteed the first hydrotreated naphtha fraction simultaneously is lower than 3PPm, the second hydrogenated diesel oil fraction is higher than 33 target;
3. adopt the present invention, do and select the operational condition of first hydrogenation reaction part by controlling the first hydrocarbon fraction, at first hydrogenation unit, make that heavy hydrocarbons is the first hydrogenated diesel oil fraction in first hydrogenation reaction effluent, thereby avoid the sepn process of the first hydrogenated diesel oil fraction and heavy oil fraction, simplify flow process greatly, reduce separating energy consumption significantly;
4. because there are certain demixing phenomenon in the first hydrocarbon fraction and the second hydrocarbon fraction when coexist in storage tank, the present invention adopts and stores respectively, the method for hydrotreating of feed has been stablized reaction feed character respectively, but stopping reaction is operated;
5. recycle hydrogen common recycle hydrogen compressor has realized that raw material classification Unionfining transforms, and has simplified flow process.
Embodiment two
Compare with embodiment one, the 3rd hydrogenation reaction effluent is incorporated into the second high pressure separate part to present embodiment and the second hydrogenation reaction effluent combined separation reclaims, to simplify the second hydrogenation reaction effluent Separation and Recovery flow process.Whole second hydrogenation heavy oil circulations have constituted whole circulation cracking flow processs.
Embodiment three
Compare with embodiment one, the beds inlet that present embodiment is incorporated into the 3rd hydrogenation reaction effluent behind the catalyst for demetalation bed of second hydrogenation reaction part contacts with described beds.Whole second hydrogenation heavy oil circulations constitute whole circulation cracking flow processs.Utilize second hydrogenation reaction part that the 3rd hydrogenation reaction effluent is carried out hydrofining, and utilize the 3rd hydrogenation reaction effluent to increase the second hydrogenation reaction portion of hot capacity, reduce by the second hydrogenation reaction part temperature rise, stable operation.The 3rd hydrogenation reaction part is not used the back catalyst for refining.
Embodiment four
Under the prerequisite of embodiment three, present embodiment is to the further refining nitrogen content that reduces of high nitrogen-containing second hydrotreated naphtha.
In the separating of oil part of second high score, obtain low nitrogen content second hydrotreated naphtha, high nitrogen-containing second hydrotreated naphtha; At least a portion high nitrogen-containing second hydrotreated naphtha goes first hydrogenation reaction part to contact with first Hydrobon catalyst.
Although this paper only enumerates four embodiment, be enough to show effect of the present invention.
Table 1 coal tar character
| Stock oil | Stock oil |
| Density (20 ℃), g/cm 3Boiling range, ℃ IBP/10% 30%/50% 70%/90% 95% viscosity, 40 ℃, mm 2/s ??100℃，mm 2/ s condensation point, ℃ carbon residue, m% ash content, m% mechanical impurity, % S, m% N, m% C, m% H, m% metal content, μ g/g Cu Ca Mg Ni V Fe Na | ??1.04 ??130/214 ??291/357 ??417/475 ??＜545 ??6.2 ??26 ??5.40 ??0.20 ??0.16 ??0.86 ??82.4 ??6.9 ??＜0.01 ??27.6 ??4.7 ??0.8 ??0.12 ??46.4 ??3.7 |
Table 2-1 first hydrogenation reaction part is formed with catalyzer
| The catalyzer classification | Metal remover | Hydrogenation deoxidation | Hydrofining |
| Chemical constitution, m% WO 3??MoO 3The NiO molecular sieve | ??6.0～8.0 ??1.5～2.5 | ??5～7 ??3～4 ??1.5～2.5 | ??17～21 ??8～10 ??3.5～5.5 |
| Carrier | ??γ-Al 2O 3 | ??γ-Al 2O 3 | |
| Auxiliary agent, wt% | ??P 2O 5：3～4.5 |
Table 2-2 second hydrogenation reaction is partly used the physico-chemical property of catalyzer
| Catalyzer | Hydrofining agent A | Hydrofining agent B | Hydrofining agent C | Hydrofining agent D |
| Shape | Raschig ring | Raschig ring | Trifolium | Trifolium |
| Metal content MoO 3??WO 3??NiO | ??4.0～5.0 ??- ??- | ??5.0～7.0 ??- ??1.5～2.5 | ??8.0～9.5 ??- ??1.5～2.5 | ??24.0～25.0 ??- ??3.3～4.2 |
Table 2-2 the 3rd hydrogenation reaction is partly used the physico-chemical property of catalyzer
| Catalyzer | Hydrofining and back are refining | Hydrocracking |
| Shape | Trifolium | Cylinder |
| Metal content MoO 3??WO 3??NiO | ??24.0～25.0 ??- ??3.3～4.2 | ??- ??23.0～26.0 ??6.2～7.3 |
Table 3 operational condition and product property table
| Project | Embodiment |
| The first hydrogenation reaction part | |
| Reaction pressure, MPa | ??18～19 |
| Temperature of reaction, ℃ metal remover+reductor/finishing agent | ??260～305/305～385 |
| The first Hydrobon catalyst volume space velocity, h -1 | ??0.3～0.36 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ??2000 |
| The first hydrotreated naphtha nitrogen content, μ g/g | ??≯3.0 |
| The first hydrogenated diesel oil cetane value | ??≮35.0 |
| The second hydrogenation reaction part | |
| Reaction pressure, MPa | ??18～19 |
| Temperature of reaction, ℃ protective material+take off carbon residue agent/finishing agent | ??310～370/370～400 |
| The second Hydrobon catalyst volume space velocity, h -1 | ??0.30～0.36 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ??2000 |
| The second hydrogenated diesel oil cetane value | ??≮33 |
| The 3rd hydrogenation reaction part | |
| Reaction pressure, MPa | ??18～19 |
| Temperature of reaction, ℃ | ??400～410 |
| The 3rd hydrocracking catalyst volume space velocity, h -1 | ??0.42～0.50 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ??1500 |
| The 3rd hydrogenated diesel oil cetane value | ??≮42 |
。
Claims (18)
1, a kind of converting and combining method for hydrogenation of coal tar distillate with different boiling ranges comprises the steps:
At first hydrogenation unit, in the first hydrogenation reaction part, mainly the first hydrocarbon fraction of being made up of the coal tar light fraction is finished first hydrogenation reaction and is converted into first hydrogenation reaction effluent, and first hydrogenation conditions is: temperature is that 200～460 ℃, pressure are that 4.0～30.0MPa, the first Hydrobon catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1; At the first high pressure separate part, separate first hydrogenation reaction effluent and obtain the first high score gas, first high score oil and the first high score water; In the separating of oil part of first high score, separate the first high score oil and obtain products such as first hydrogenated diesel oil; At least a portion first high score gas enters first hydrogenation reaction and partly does the use of first recycle hydrogen;
At second hydrogenation unit, in the second hydrogenation reaction part, main finish second hydrogenation reaction by the second hydrocarbon fraction of coal tar heavy duty fractional composition and be converted into second hydrogenation reaction effluent, second hydrogenation conditions is: temperature is that 220～480 ℃, pressure are that 4.0～30.0MPa, the second Hydrobon catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1; At the second high pressure separate part, separate second hydrogenation reaction effluent and obtain the second high score gas, second high score oil and the second high score water; In the separating of oil part of second high score, obtain products such as second hydrogenated diesel oil, the second hydrogenation heavy oil; At least a portion second high score gas enters second hydrogenation reaction and partly does the use of second recycle hydrogen;
First recycle hydrogen and the second recycle hydrogen common recycle hydrogen compressor.
2, method according to claim 1 is characterized in that:
In the separating of oil part of second high score, obtain the second hydrogenation light fraction oil, at least a portion second hydrogenation light fraction oil enters first hydrogenation reaction part and contacts with first Hydrobon catalyst.
3, method according to claim 1 is characterized in that:
In the separating of oil part of second high score, obtain low nitrogen content second hydrotreated naphtha and high nitrogen-containing second hydrotreated naphtha, at least a portion high nitrogen-containing second hydrotreated naphtha enters first hydrogenation reaction part and contacts with first Hydrobon catalyst.
4, method according to claim 1 is characterized in that:
In the separating of oil part of second high score, enter second light pressure separator after the oil decompression of second high score and be separated into second low pressure gas and the second low oil that divides, second low divide oil enter second low divide oily separation column to be separated into second low to divide oil content to heat up in a steamer column overhead gas, heavy hydrocarbons be that second of hydrogenated diesel oil fraction lowly divides oil content to heat up in a steamer column overhead oil and the second low oil content that divides heats up in a steamer oil at the bottom of the Tata; At least a portion second low branch oil content heats up in a steamer column overhead oil and enters the separating of oil part of first high score.
5, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that:
Heavy hydrocarbons is the hydrogenated diesel oil fraction in the first high score oil.
6, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that:
First hydrogenation conditions is: temperature is that 200～430 ℃, pressure are that 6.0～25.0MPa, the first Hydrobon catalyst volume space velocity are 0.05～4.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1;
Second hydrogenation conditions is: temperature is that 240～430 ℃, pressure are that 6.0～25.0MPa, the second Hydrobon catalyst volume space velocity are 0.05～4.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
7, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that:
The nitrogen content of hydrotreated naphtha (mean value) is lower than 10PPm;
The cetane value of hydrogenated diesel oil (mean value) is higher than 30.
8, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that:
The nitrogen content of hydrotreated naphtha (mean value) is lower than 4PPm;
The cetane value of hydrogenated diesel oil (mean value) is higher than 35.
9, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that:
At the coal tar separate part, separate original coal tar and obtain the first hydrocarbon fraction and the second hydrocarbon fraction, the first hydrocarbon fraction and the second hydrocarbon fraction go first hydrogenation reaction part and the second hydrogenation reaction part respectively.
10, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that:
At the coal tar separate part, separate original coal tar and obtain the first hydrocarbon fraction, second hydrocarbon fraction and the coal-tar pitch, the first hydrocarbon fraction and the second hydrocarbon fraction go first hydrogenation reaction part and the second hydrogenation reaction part respectively.
11, method according to claim 1 is characterized in that:
In the 3rd hydrogenation reaction part, the second hydrogenation heavy oil is finished the 3rd hydrogenation reaction and is converted into the 3rd hydrogenation reaction effluent, and the 3rd hydrogenation conditions is: temperature is that 280～480 ℃, pressure are that 4.0～30.0MPa, the 3rd hydrocracking catalyst volume space velocity are 0.05～5.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1.
12, method according to claim 11 is characterized in that:
The 3rd hydrogenation conditions is: temperature is that 350～460 ℃, pressure are that 6.0～25.0MPa, the 3rd hydrocracking catalyst volume space velocity are 0.1～2.0hr
-1, hydrogen/stock oil volume ratio is 1000: 1～3000: 1.
13, according to claim 11 or 12 described methods, it is characterized in that:
At the 3rd high pressure separate part, separate the 3rd hydrogenation reaction effluent and obtain the 3rd high score gas, the 3rd high score oil;
At least a portion the 3rd high score gas enters the 3rd hydrogenation reaction and partly does the use of the 3rd recycle hydrogen;
First recycle hydrogen, second recycle hydrogen and the 3rd recycle hydrogen common recycle hydrogen compressor.
In the separating of oil part of the 3rd high score, obtain products such as the 3rd hydrogenated diesel oil.
14, according to claim 11 or 12 described methods, it is characterized in that:
In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenation heavy oil, at least a portion the 3rd hydrogenation heavy oil goes second hydrogenation reaction part to contact with second Hydrobon catalyst.
15, according to claim 11 or 12 described methods, it is characterized in that:
In the separating of oil part of the 3rd high score, obtain the 3rd hydrogenation heavy oil, at least a portion the 3rd hydrogenation heavy oil goes the 3rd hydrogenation reaction part to contact with the 3rd hydrocracking catalyst.
16, according to claim 11 or 12 described methods, it is characterized in that:
The 3rd hydrogenation reaction effluent enters the separating of oil part of second high score.
17, according to claim 11 or 12 described methods, it is characterized in that:
The 3rd hydrogenation reaction effluent enters second hydrogenation reaction part and contacts with second Hydrobon catalyst.
18, according to claim 11 or 12 described methods, it is characterized in that:
The beds inlet that the 3rd hydrogenation reaction effluent enters behind second hydrogenation reaction catalyst for demetalation bed partly contacts with described beds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810170910 CN101629103B (en) | 2008-10-15 | 2008-10-15 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810170910 CN101629103B (en) | 2008-10-15 | 2008-10-15 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101629103A true CN101629103A (en) | 2010-01-20 |
| CN101629103B CN101629103B (en) | 2013-07-17 |
Family
ID=41574387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810170910 Active CN101629103B (en) | 2008-10-15 | 2008-10-15 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101629103B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864327A (en) * | 2010-04-29 | 2010-10-20 | 长岭炼化岳阳工程设计有限公司 | Coal tar hydrogenation modification method |
| CN102399584A (en) * | 2011-10-12 | 2012-04-04 | 中国石油化工股份有限公司 | Hydrogen combined optimized utilization technology of hydrogenation apparatus |
| CN103540352A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Coal tar processing method for increasing yield of light oils |
| CN103540351A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined technique for processing full fraction of coal tar |
| CN103540353A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined hydrogenation process method for treating coal tar and residual oil |
| CN103789032A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil |
| CN103789034A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce large-specific weight aviation kerosene |
| CN104277876A (en) * | 2013-07-05 | 2015-01-14 | 任相坤 | Inferior oil two-stage slurry bed hydrogenation technology |
| CN104277878A (en) * | 2013-07-05 | 2015-01-14 | 任相坤 | Two-stage slurry bed hydrogenation process of high temperature coal tar |
| CN105419835A (en) * | 2015-11-30 | 2016-03-23 | 华电重工股份有限公司 | Processing method of coal low-temperature pyrolysis volatile component |
| CN105861044A (en) * | 2016-03-21 | 2016-08-17 | 何巨堂 | Combination method for hydrogen compressors used in hydroconversion of different raw hydrocarbon materials |
| CN114426880A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Fixed bed residual oil hydrogenation method for producing catalytic cracking raw material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240192B (en) * | 2007-02-09 | 2011-08-24 | 中国石油化工股份有限公司 | Method for producing high grade diesel oil by coal tar heavy fractioning hydrogenation |
-
2008
- 2008-10-15 CN CN 200810170910 patent/CN101629103B/en active Active
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864327A (en) * | 2010-04-29 | 2010-10-20 | 长岭炼化岳阳工程设计有限公司 | Coal tar hydrogenation modification method |
| CN102399584A (en) * | 2011-10-12 | 2012-04-04 | 中国石油化工股份有限公司 | Hydrogen combined optimized utilization technology of hydrogenation apparatus |
| CN102399584B (en) * | 2011-10-12 | 2014-06-25 | 中国石油化工股份有限公司 | Hydrogen combined optimized utilization technology of hydrogenation apparatus |
| CN103540352A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Coal tar processing method for increasing yield of light oils |
| CN103540351A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined technique for processing full fraction of coal tar |
| CN103540353A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined hydrogenation process method for treating coal tar and residual oil |
| CN103789034B (en) * | 2012-11-05 | 2015-04-01 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce large-specific weight aviation kerosene |
| CN103789032A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil |
| CN103789034A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce large-specific weight aviation kerosene |
| CN103789032B (en) * | 2012-11-05 | 2015-04-15 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil |
| CN104277876A (en) * | 2013-07-05 | 2015-01-14 | 任相坤 | Inferior oil two-stage slurry bed hydrogenation technology |
| CN104277878A (en) * | 2013-07-05 | 2015-01-14 | 任相坤 | Two-stage slurry bed hydrogenation process of high temperature coal tar |
| CN104277876B (en) * | 2013-07-05 | 2016-04-13 | 任相坤 | A kind of two-stage slurry bed system hydrogenation technique of poor quality oil |
| CN104277878B (en) * | 2013-07-05 | 2016-05-11 | 任相坤 | A kind of two-stage slurry state bed hydroprocessing technique of high temperature coal-tar |
| CN105419835A (en) * | 2015-11-30 | 2016-03-23 | 华电重工股份有限公司 | Processing method of coal low-temperature pyrolysis volatile component |
| CN105861044A (en) * | 2016-03-21 | 2016-08-17 | 何巨堂 | Combination method for hydrogen compressors used in hydroconversion of different raw hydrocarbon materials |
| CN114426880A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Fixed bed residual oil hydrogenation method for producing catalytic cracking raw material |
| CN114426880B (en) * | 2020-09-28 | 2023-12-12 | 中国石油化工股份有限公司 | Fixed bed residuum hydrogenation method for producing catalytic cracking raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101629103B (en) | 2013-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101629103B (en) | Hydro-conversion combination method for coal tar fraction with different boiling ranges | |
| CN101495601B (en) | Process for the hydrotreatment of a gas-oil feedstock, hydrotreatment reactor for implementing the process, and corresponding hydrorefining unit | |
| CN101712886A (en) | Method for hydrogenating coal tar | |
| CN101831317A (en) | Hydrogenation method of hydrocarbon with high contents of aryl and nitrogen | |
| CN101024780A (en) | Method for hydrogenation cracking anthracent | |
| CN101892077B (en) | Two-stage hydrocarbon hydrogenation method with serial high-pressure parts | |
| CN102585897B (en) | Method for conversion of low-hydrogen heavy oil to light fractions by hydrogenation with hydrogen-supplying hydrocarbons | |
| CN102051222A (en) | High-nitrogen high-aromatic-oil hydrogenation conversion method based on two-stage process | |
| CN101033409A (en) | Method of hydrogenation conversion for anthracene oil | |
| CN102071057A (en) | Two-stage high-nitrogen high-aromatic oil hydro-conversion method | |
| CN101629101A (en) | Hydro-conversion combination method for coal tar fraction with different boiling ranges | |
| CN103740404A (en) | High-nitrogen high-aromatic hydrocarbon hydrogenation modification method | |
| CN103897730A (en) | Inferior hydrocarbon hydro-upgrading method comprising raw material shunt series prehydrogenation process | |
| CN103333713A (en) | High-nitrogen high-aromatic-hydrocarbon hydro-upgrading and thermal-cracking combined method | |
| CN103820147A (en) | High-nitrogen and high-aromatic hydrocarbon hydrogenation conversion method | |
| CN102433156B (en) | A kind of different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation transforms combined method | |
| CN101717660A (en) | Method for hydrogenating hydrocarbon | |
| CN102021029A (en) | Two-stage process high aromatic oil hydro-conversion method | |
| CN102585898A (en) | High-nitrogen high-aromatic-oil two-stage method hydrocarbon hydrogenation method | |
| CN102021027A (en) | Two-stage hydrocarbon hydrogenation method for cracking different fractions of generated oil at refining stage in branches | |
| CN102021028A (en) | Hydro-conversion method of two-stage method aromatic oil | |
| CN102311782B (en) | Method for producing diesel oil by purifying coal tar through hydrogenating | |
| CN101041783B (en) | Coal tar hydro-conversion method | |
| CN101629104B (en) | Hydro-conversion combination method for coal tar fraction with different boiling ranges | |
| CN101629100B (en) | Hydrogenation combination method comprising process of coal tar hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |