CN101712887A - Hydrocarbon hydrogenating method - Google Patents
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- CN101712887A CN101712887A CN200910174845A CN200910174845A CN101712887A CN 101712887 A CN101712887 A CN 101712887A CN 200910174845 A CN200910174845 A CN 200910174845A CN 200910174845 A CN200910174845 A CN 200910174845A CN 101712887 A CN101712887 A CN 101712887A
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Abstract
The invention relates to a hydrocarbon hydrogenating method which adopts a two-section method to connect hydrogenation techniques in series. Raw material hydrocarbon is subject to hydrogenation refining section, macromolecule oil enters into the catalyst bed layer of the hydrocracking section, and the hydrocracking section macromolecule oil is separated to obtain the hydrogenation fraction product. Furthermore, a thermal high pressure separator is arranged in the hydrogenation refining section, and the hydrogenation refining thermal macromolecule oil enters into the catalyst bed layer of the hydrocracking section. When the hydrocracking distillate circulates to the catalyst bed layer of the hydrogenation refining section and/or the catalyst bed layer of the hydrocracking section, a circulation process is formed. The invention provides a two-section method hydrogenation method with simple process, little investment, low energy consumption and flexible circulation to anthracene oil hydrogenation, and is suitable for improvement of newly built devices and existing devices.
Description
Technical field
The present invention relates to a kind of hydrocarbon hydrogenating method; Say especially and the present invention relates to a kind of high nitrogen, high aromatic oil two-stage method method for hydrogenation such as carbolineum; More particularly the present invention relates to a kind of carbolineum two-stage method " hydrofining+hydrocracking " and produce the method for diesel component.
Background technology
The inventor's following patent application document formerly relates to carbolineum hydrogenation notion:
Sequence number patent document title application number publication number
1. a kind of carbolineum method for hydrogen cracking 200810149874.8 CN101024780A
2. a kind of carbolineum method for hydrogenation 200810171313.8 CN101033409A
3. a kind of method for hydrogenating coal tar 200610071230.2 CN101041783A
CN101024780A discloses a kind of carbolineum method for hydrogen cracking, adopt hydrofining-hydrocracking one-stage serial flow process, because the alkaline ammonia in the carbolineum hydrofining reaction effluent has entered the hydrocracking catalyst bed, has greatly suppressed the cracking catalyst cracking performance.
CN101033409A discloses a kind of carbolineum method for hydrogen cracking, adopt two-stage method serial hydrogenation technology, carbolineum hydrofining generates oil obtains removing ammonia, hydrogen sulfide, low boiling hydrocarbon through separation first last running of mainly being made up of greater than 200 ℃ last running conventional boiling point, first last running enters the hydrocracking catalyst bed, owing to use hydrofining to generate separating of oil part, the flow process complexity, investment is high.
CN101041783A discloses a kind of method for hydrogenating coal tar that can be used for the carbolineum hydrogenation process, and coal tar raw material is converted into first reaction effluent in first reactive moieties, and first reaction effluent obtains the first hot high score oil in the separation of the first thermal high separate part; The first hot high score oil is converted into second reaction effluent in second reactive moieties.Since use the separating of oil part of the first cold high score, the flow process complexity, and investment is high.
There are following characteristics in the carbolineum hydrogenation process:
1. in the hydrofining reaction effluent ammonia content far above hydrogen sulfide content, wash the ammonia process in the water filling of hydrofining reaction effluent, overwhelming majority ammonia and hydrogen sulfide have all entered hydrofining and have divided in the cold high pressure separator sour water, and ammonia and hydrogen sulfide content are seldom in the hydrofining cold high pressure separator high score oil; As the hydrofining high pressure hot separator is set, owing to temperature height, a large amount of hydrogen exist, ammonia and hydrogen sulfide content are also seldom in the hot high score oil of hydrofining;
2. the lower boiling product of carbolineum unifining process (conventional gas hydrocarbon and gasoline fraction) proportion is not more than 20% usually, generally is not more than 15%, and these components are when contacting with the amorphous hydrocracking catalyst of amorphous or low molecular sieve content, the very poor or not cracking substantially of cracking performance;
3. the conventional boiling point of carbolineum unifining process is higher than 200 ℃ hydrocarbon component, character poor (density is big, cetane value is low, nitrogen content high), just can be converted into diesel component through hydrocracked, treated, hydrocracking process need use have certain anti-nitrogen/anti-ammonia ability amorphous hydrocracking catalyst or the amorphous hydrocracking catalyst contact of low molecular sieve content.
Therefore, the present invention proposes a kind of two-stage method carbolineum method for hydrogenation that hydrofining generates separating of oil part of not establishing, and this method is not appeared in the newspapers.
For the hydrocarbon ils with above-mentioned three characteristics, the present invention is suitable for.
Therefore, first purpose of the present invention is to provide a kind of two-stage method carbolineum method for hydrogenation that hydrofining generates separating of oil part of not establishing; Second purpose of the present invention is to provide a kind of two-stage hydrocarbon hydrogenation method that hydrofining generates separating of oil part of not establishing.
Summary of the invention
A kind of hydrocarbon hydrogenating method of the present invention is characterized in that comprising following steps:
1. in first reactive moieties, under hydrogen and Hydrobon catalyst existence condition, first raw material hydrocarbon is finished hydrofining reaction, generates first reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon;
2. at the first cold anticyclone separate part, first reaction effluent cooling and being separated into after the water filling: first a cold high score gas of mainly forming by hydrogen, a first cold high score oil of mainly forming by conventional gas hydrocarbon, conventional liq hydrocarbon and dissolved hydrogen, first a cold high score water of mainly forming by water, dissolved ammonia and dissolved hydrogen sulfide;
3. at least a portion described first cold high score gas gas returns first reactive moieties;
4. in second reactive moieties, under hydrogen and hydrocracking catalyst existence condition, at least a portion described first cold high score oil is finished hydrocracking reaction, generates second reaction effluent of being made up of hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon;
5. at the second cold anticyclone separate part, described second reaction effluent cooling also is separated into: second a cold high score gas of mainly being made up of hydrogen, second a cold high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.
Feature of the present invention further is: first raw material hydrocarbon is the hydrocarbon based on carbolineum.
Feature of the present invention further is: first raw material hydrocarbon is a carbolineum.
Operational condition of the present invention is: the first reactive moieties operational condition is: temperature is that 250～480 ℃, pressure are that 6.0～30.0MPa, catalyst for refining volume space velocity are 0.05～15hr
-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1; The second reactive moieties operational condition is: in temperature is that 300～480 ℃, pressure are that 6.0～30.0MPa, cracking catalyst volume space velocity are 0.05～15hr
-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.
The preferable operational condition of the present invention is: the first reactive moieties operational condition is: temperature is that 320～415 ℃, pressure are that 10.0～25.0MPa, catalyst for refining volume space velocity are 0.2～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1; The second reactive moieties operational condition is: 330～440 ℃, pressure are that 10.0～25.0MPa, cracking catalyst volume space velocity are 0.4～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.
The productive target of first reactive moieties is normally: hydrofining gives birth to that olefiant nitrogen content is reduced to that 1500PPm is following, hydrofining gives birth to that olefiant sulphur content is reduced to that 400PPm is following, the first raw material hydrocarbon carbon residue decreasing ratio is greater than 70%.
The productive target preferably of first reactive moieties is: hydrofining gives birth to that olefiant nitrogen content is reduced to that 800PPm is following, hydrofining gives birth to that olefiant sulphur content is reduced to that 300PPm is following, the first raw material hydrocarbon carbon residue decreasing ratio is greater than 90%.
The productive target of first reactive moieties is preferably: hydrofining gives birth to that olefiant nitrogen content is reduced to that 400PPm is following, hydrofining gives birth to that olefiant sulphur content is reduced to that 200PPm is following, the first raw material hydrocarbon carbon residue decreasing ratio is greater than 95%.
The productive target of second reactive moieties is normally: hydrocracking is given birth to olefiant 95% and is distillated a temperature and distillate a temperature than 95% of first raw material hydrocarbon and hang down more than 60 ℃.
The productive target preferably of second reactive moieties is: hydrocracking is given birth to olefiant 95% and is distillated a temperature and distillate a temperature than 95% of first raw material hydrocarbon and hang down more than 100 ℃.
The productive target of second reactive moieties is preferably: hydrocracking is given birth to olefiant 95% and is distillated a temperature and distillate a temperature than 95% of first raw material hydrocarbon and hang down more than 125 ℃.
In order to reduce by the first reaction effluent calorific loss, feature of the present invention further is: first reaction effluent enters the first thermal high separate part and is separated into: first a hot high score gas of mainly being made up of hydrogen, first a hot high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.The first hot high score gas enters the first cold anticyclone separate part, and the first hot high score oil enters second reactive moieties and contacts with hydrocracking catalyst.The first thermal high separate part service temperature is generally 150～380 ℃, is generally 200～280 ℃.
In order to reduce by the second reaction effluent calorific loss, feature of the present invention further is: second reaction effluent enters the second thermal high separate part and is separated into: second a hot high score gas of mainly being made up of hydrogen, second a hot high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.The second hot high score gas enters the second cold anticyclone separate part.The second thermal high separate part service temperature is generally 150～380 ℃, is generally 200～280 ℃.
Feature of the present invention further is: separate second reactive moieties generation oil and obtain the narrow fraction oil product, the narrow fraction oil product that at least a portion boiling range is the highest is circulated to the Hydrobon catalyst bed and does the use of second raw material hydrocarbon.
Feature of the present invention further is: separate second reactive moieties generation oil and obtain the narrow fraction oil product, the narrow fraction oil product that at least a portion boiling range is the highest is circulated to the hydrocracking catalyst bed.
Feature of the present invention further is: entering after the decompression of second cold high score oil at pressure is that 0.4～4.0MPa, temperature are the second cold low separator of operating under 30～70 ℃ the condition and are separated into the second cold low separator gas and the second cold low separator liquid; The part second cold low separator liquid is circulated to the second cold anticyclone separate part and contacts with gas in second reaction effluent.
Feature of the present invention further is: hydrofining reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
Feature of the present invention further is: hydrofining intermediate reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
Feature of the present invention further is: hydrocracking reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
Feature of the present invention further is: hydrocracking intermediate reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
Feature of the present invention further is: the part first hot high score oil enters first reactive moieties and contacts with Hydrobon catalyst.
Feature of the present invention further is: raw material carbolineum is dehydration carbolineum.
Embodiment
Below describe the present invention in detail.
Pressure of the present invention is absolute pressure.
Conventional boiling point of the present invention refers to the vapor-liquid equilibrium temperature of material under a barometric point.
Conventional gas hydrocarbon of the present invention refers to and is the gasiform hydro carbons under the normal condition, comprises methane, ethane, propane, butane.
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.
Petroleum naphtha of the present invention refers to conventional boiling point and is lower than 200 ℃ conventional liq hydrocarbon.
It is 200～375 ℃ hydro carbons that diesel component of the present invention refers to conventional boiling point.
Impurity composition of the present invention refers to the hydride of non-hydrocarbon component in the stock oil such as water, ammonia, hydrogen sulfide etc.
The composition of component of the present invention or concentration or content or yield value unless stated otherwise, are the weight basis value.
Two-stage method hydrogenation of the present invention, the hydrotreatment process that refers to feedstock conversion and be the finished product comprise two hydrogenation reaction systems (first hydrogenation reaction system and second hydrogenation reaction system) and the supporting separating of oil part of generation (second generate separating of oil part and may exist first generate separating of oil part).Two hydrogenation reaction systems form overall serial flow on the stock oil flow process.Two-stage method hydrogenation process of the present invention can be cancelled and generates first of separating of oil common use fractionating tower equipment for the narrow fraction oil product with first and generate separating of oil part.
Hydrofining of the present invention generates oil, refers in first reaction effluent and transforms the conventional liq hydrocarbon that produces by initial feed (such as the carbolineum raw material).
Hydrocracking of the present invention generates oil, refers to the conventional liq hydrocarbon in second reaction effluent.
First raw material hydrocarbon of the present invention has following characteristics usually:
1. in the first raw material hydrocarbon hydrofining reaction effluent ammonia content far above hydrogen sulfide content, wash the ammonia process in the water filling of hydrofining reaction effluent, overwhelming majority ammonia and hydrogen sulfide have all entered hydrofining and have divided in the cold high pressure separator sour water, and ammonia and hydrogen sulfide content are seldom in the hydrofining cold high pressure separator high score oil; As the hydrofining high pressure hot separator is set, owing to temperature height, a large amount of hydrogen exist, ammonia and hydrogen sulfide content are also seldom in the hot high score oil of hydrofining;
2. the lower boiling product of the first raw material hydrocarbon unifining process (conventional gas hydrocarbon and gasoline fraction) proportion is not more than 20% usually, generally is not more than 15%, and these components are when contacting with the amorphous hydrocracking catalyst of amorphous or low molecular sieve content, the very poor or not cracking substantially of cracking performance;
3. the conventional boiling point of the first raw material hydrocarbon unifining process is higher than 200 ℃ hydrocarbon component, character poor (density is big, cetane value is low, nitrogen content high), just can be converted into diesel component through hydrocracked, treated, hydrocracking process need use have certain anti-nitrogen/anti-ammonia ability amorphous hydrocracking catalyst or the amorphous hydrocracking catalyst contact of low molecular sieve content.
First raw material hydrocarbon can be based on the hydrocarbon of carbolineum.
Hydrocarbon based on carbolineum can be carbolineum or carbolineum cut or carbolineum processing (such as hot-work such as coking, visbreakings) gained cut or their mixture.
First reactive moieties in processing first raw material hydrocarbon, can be processed second raw material hydrocarbon.
Second raw material hydrocarbon, can be petroleum base hydrocarbon or shale oil base hydrocarbon or coal-tar base hydrocarbon, also can be to generate separating of oil gained narrow fraction oil (being generally the boiling point soprano) from the hydrocarbonaceous stream of the first raw material hydrocarbon hydrogenation process such as the hot high score oil of hydrofining or the hot high score oil of hydrocracking or the cold high score oil of hydrocracking or the low oil or the cold low branch oil of hydrocracking or hydrocracking of dividing of hydrocracking heat.
Describe the present invention in detail below in conjunction with the carbolineum hydrogenation process.
According to the present invention, one section hydrofining reaction of finishing carbolineum raw material (first raw material hydrocarbon) separates with the cold anticyclone of hydrofining reaction effluent, and at least a portion described first cold high score oil uses as two sections stock oil; Finish hydrocracking reaction and hydrocracking generation oil separating, obtain diesel oil distillate and two sections other products for two sections.
Carbolineum as first raw material hydrocarbon of the present invention can be the anthracene oil product from pyrolysis of coal or other process.Coal tar carbolineum of the present invention refers to: lightweight carbolineum (mainly by 300～360 ℃ of fractions consistings), heavy carbolineum (mainly by 360～500 ℃ of fractions consistings) and mixing oil thereof.Because raw coal character and coke making process condition all change within the specific limits, the character of coal-tar heavy oil also changes within the specific limits.The processing condition of coal-tar heavy oil primary distillation process and product requirement also change within the specific limits, so the character of coal-tar heavy oil carbolineum also changes within the specific limits.The character of carbolineum, proportion is generally 1.02～1.25, conventional boiling point is generally 210～500 ℃ and is generally 300～480 ℃, usually metal content is that 10～80PPm, sulphur content are 0.4～0.8%, nitrogen content is 0.6～1.4%, oxygen level is 0.4～1.8%, and water-content is 0.2～5.0% usually.
Table 1 one-level carbolineum and secondary carbolineum technical indicator (country code: GB/8353-87)
| Index name | One-level | Secondary |
| Density (20 ℃), g/m 3 | ??1.07 | ??1.07 |
| Moisture content, % | ??≤0.5 | ??≤0.8 |
| Viscosity, mm 2/s | ??≤1.9 | ??≤1.9 |
| Boiling range: quantity of distillate before 210 ℃, % | ??≤5 | ??≤5 |
| Quantity of distillate before 360 ℃, % | ??≥65 | ??≥60 |
In the hydrofining of carbolineum, particularly hydrocracking process, water is disadvantageous component, on the one hand, enter in the heat temperature raising process of hydrogenator at carbolineum, the existence of water can aggravate in the carbolineum acids to the corrosion of pipeline, equipment etc., the iron ion that corrosion produces enters hydrofining reactor, for guaranteeing the operational cycle of expection, must use more hydrogenation deferrization catalyzer (protective material) to increase the hydrogen consumption simultaneously; On the other hand, the increase of raw water content will improve the reaction process steam partial pressure, and will be unfavorable to catalyst performance stabilised and long-term operation.Therefore, before carbolineum enters first hydrogenation reaction part, carry out processed usually to reduce water-content as much as possible, the carbolineum dehydration method is unrestricted.
Carbolineum dehydration method commonly used is a decompression dehydration behind the heat temperature raising: earlier carbolineum (is heated to 80～200 ℃ preferably 100～160 ℃ such as pressure-controlling 0.5～1.0MPa) under certain pressure, enter then at negative pressure (as pressure-controlling in 0.025～0.05MPa (the absolute pressure)) water trap (flash tank or dehydration tower) of operation down, the water vapor of oily is discharged the water trap top, enter the liquid collecting jar and discharge system then after the condensation cooling, the liquid collecting jar links to each other with the decompression vacuum pumping system.Dehydration carbolineum is discharged from the water trap bottom.
Industry carbolineum also contains harmful solid particulate (such as the solid particulate of diameter greater than 10～20 microns) usually; in order to prevent that harmful solid particulate from damaging the carbolineum high-pressure delivery pump and be deposited on the beds in the reactor, under the forward and backward proper temperature condition of carbolineum dehydration, carry out carbolineum usually and filter.
The present invention advises that industrial carbolineum dewaters and filtration treatment before entering the hydrogenation reaction part.
According to the present invention, in first reactive moieties, under hydrogen and Hydrobon catalyst existence condition, first raw material hydrocarbon (carbolineum) is finished hydrofining reaction, generates first reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon;
The operational condition of first reactive moieties is generally: temperature is that 250～480 ℃, pressure are that 6.0～30.0MPa, catalyst for refining volume space velocity are 0.05～15hr
-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.
The operational condition of first reactive moieties, the preferably is: temperature is that 320～415 ℃, pressure are that 10.0～25.0MPa, catalyst for refining volume space velocity are 0.2～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.
The operational condition of first reactive moieties is preferably: temperature is that 360～400 ℃, pressure are that 12.0～18.0MPa, catalyst for refining volume space velocity are 0.4～1.4hr
-1, hydrogen/stock oil volume ratio is 800: 1～1800: 1.
Carbolineum unifining process one speech of the present invention, refer to the reaction process of the consumption hydrogen that carbolineum takes place under hydrogen and appropriate catalyst existence condition, its minimum reaction depth should possess MIN industrial significance: be second reactive moieties suitable hydrocracking raw material oil is provided, should determine the requirement of feedstock property according to raw material carbolineum character and cracking catalyst: generally this process is reduced to the living olefiant nitrogen content of hydrofining below the 1500PPm, is reduced to usually below the 800PPm, preferably is reduced to below the 400PPm; General this process is given birth to olefiant sulphur content with hydrofining 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 raw material carbolineum greater than 70%, usually greater than 90%, more preferably greater than 95%, to delay the knot charcoal speed of the second reactive moieties hydrocracking catalyst, prolong the operational cycle of the second reactive moieties cracking catalyst.
Described first reactive moieties, different because of the difference of carbolineum feedstock property (metal content, oxygen level, sulphur content, nitrogen content, aromaticity content, boiling range, proportion) and the hydrofining degree of depth (hydrodemetallation (HDM), hydrogenation deoxidation, hydrogenating desulfurization, hydrodenitrification, hydrogenation be saturated, to a certain degree hydrocracking), the variation range of its operational condition is very wide, should determine according to concrete carbolineum unifining process condition.
Described first reactive moieties, the Hydrobon catalyst of use can be the series combinations of one or both or multiple catalyzer and load in mixture.Hydrobon catalyst can be Hydrobon catalyst and combinations thereof such as the hydrogenating desulfurization agent used of the unifining process of refining of petroleum diesel oil and/or wax oil, hydrodenitrification agent, hydrogenation aromatic hydrocarbons saturator.Because the carbolineum metal content is higher usually, so before Hydrobon catalyst, use hydrogenation protecting agent (hydrodemetallation (HDM) agent).
Described first reactive moieties can add reactive moieties with any additional sulphur as required, to guarantee the necessary minimum concentration of hydrogen sulfide of reactive moieties, guarantees that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value: such as 500PPm or 1000PPm.Described additional sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide the carbolineum hydrogenation 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 first cold anticyclone separate part, first reaction effluent cooling and being separated into after the water filling: first a cold high score gas of mainly forming by hydrogen, a first cold high score oil of mainly forming by conventional gas hydrocarbon, conventional liq hydrocarbon and dissolved hydrogen, first a cold high score water of mainly forming by water, dissolved ammonia and dissolved hydrogen sulfide.
At the first cold anticyclone separate part, before first reaction effluent enters cold high pressure separator, inject washing water to reaction effluent usually.Described first reaction effluent usually earlier reduces temperature (generally being and the heat exchange of reactive moieties raw material) to about 220～100 ℃, mixes first 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 reaction effluent, and the aqueous solution behind the absorption ammonia must absorb the hydrogen sulfide in first reaction effluent.
The described first cold anticyclone separate part comprises cooling, the separating step of first reaction effluent after the water filling.At this, first reaction effluent reduces temperature (using air-cooler and or watercooler usually) earlier usually to about 30～70 ℃, best 30～60 ℃ after the described water filling, in this temperature-fall period, water vapor is condensed into liquid phase gradually in the water filling afterreaction effluent, hydrogen sulfide in ammonia in the absorption reaction product and the further absorption reaction product forms high score water liquid.First reaction effluent cooling and in first cold high pressure separator, being separated into after the final described water filling: first a cold high score gas gas of mainly forming, the main first cold high score fluid body and main first a cold high score water liquid that form by water and that be dissolved with hydrogen sulfide, ammonia of forming by conventional gas hydrocarbon, conventional liq hydrocarbon and dissolved hydrogen by hydrogen.The described first cold high score water liquid, wherein the content of ammonia is generally 1～15% (w), is preferably 3～8% (w).
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 reaction effluent, the liquid phase water yield must be greater than zero, be preferably the washing water total amount 30% or more, vaporize entirely to prevent water; On the other hand, the direct purpose of washing water is to absorb ammonia in first reaction product at the first cold anticyclone separate part, the ammonia concentration that prevents first cold anticyclone separation gas is too high, gather at first reactive system, reduce catalyst activity, the ammonia concentration that common first cold anticyclone is separated gas is low more good more, generally is not more than 200PPm, preferably is not more than 50PPm; Again on the one hand, the direct purpose of another of washing water is ammonia and the hydrogen sulfide that absorbs in first reaction product, prevents that first 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 described first cold anticyclone separate part, its separator operation pressure is that the first reactive moieties pressure deducts true pressure and falls, and the difference of the first cold anticyclone separate part working pressure and the first reactive moieties pressure should not be crossed low or too high, be generally 0.5～1.2MPa, be preferably 0.8MPa.
The described first cold high score gas 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 described first cold high score gas gas and return first reactive moieties and form circulating hydrogen, so that necessary amounts of hydrogen of first reactive moieties and hydrogen concentration to be provided; In order to improve plant investment efficient, must guarantee that the first recycle hydrogen concentration is not less than aforesaid low limit value, for this reason, distribute according to concrete feedstock property, reaction conditions, product, can get rid of a part described first cold high score gas gas (hereinafter to be referred as the first cold high score gas discharging gas) to get rid of methane, the ethane that reaction produces.Discharge gas for the first cold high score gas, can adopt conventional membrane separation process or pressure swing adsorption technique or oil wash technology to realize hydrogen-non-hydrogen gaseous fraction separation, and the hydrogen that reclaims is used as new hydrogen.
The first new hydrogen (first raw hydrogen) enters the hydrogen that first reactive moieties consumes with the postreaction process, and the first 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).
The objective of the invention is to: for giving full play to the cracking catalyst performance of second reactive moieties, the pre-treatment before first section is carried out cracking to carbolineum stock oil generates the stock oil of second reactive moieties.Metal, oxygen, sulphur, nitrogen, carbon residue in the first reactive moieties effective elimination carbolineum, make at least a portion condensed-nuclei aromatics wherein saturated, carbolineum character is improved significantly, obtained one and remove water, remove ammonia, preferably also remove the stock oil of the first cold high score oil of hydrogen sulfide as second reactive moieties.
In order to implement the present invention, before the first cold anticyclone separate part of first reaction effluent, can set up the first thermal high separate part, in this flow process, first reaction effluent is introduced into service temperature and is generally 150～380 ℃, is preferably 200～280 ℃ thermal high separate part and is separated into: first a hot high score gas gas of mainly being made up of hydrogen, main first a hot high score fluid body of being made up of conventional liq hydrocarbon and dissolved hydrogen.The first hot high score gas gas enters the first cold anticyclone separate part; The first hot high score oil is made the second reactive moieties stock oil and is used.
According to the present invention, in second reactive moieties, under hydrogen and hydrocracking catalyst existence condition, at least a portion described first cold high score oil is finished hydrocracking reaction, generates second reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.
The second reactive moieties operational condition is generally: in temperature is that 300～480 ℃, pressure are that 6.0～30.0MPa, cracking catalyst volume space velocity are 0.05～15hr
-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.
The second reactive moieties operational condition, the preferably is: 330～440 ℃, pressure are that 10.0～25.0MPa, cracking catalyst volume space velocity are 0.4～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.
The operational condition of second reactive moieties is preferably: temperature is that 350～400 ℃, pressure are that 12.0～18.0MPa, cracking catalyst volume space velocity are 0.8～1.6hr
-1, hydrogen/stock oil volume ratio is 800: 1～1800: 1.
Described second reactive moieties, different because of its raw material (the first cold high score oil) difference of character (nitrogen content, aromaticity content) and the hydrocracking degree of depth of expection, the variation range of its operational condition is very wide, should determine according to concrete process condition.
Second reactive moieties 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 hydrocracking catalyst (comprise and relax cracking catalyst) and the combination thereof that the hydrocracking process of refining of petroleum diesel oil (comprising poor ignition quality fuel) and/or wax oil uses.Can select the amorphous hydrocracking catalyst of not fusion molecular sieve or the amorphous hydrocracking catalyst of a small amount of fusion molecular sieve for use,, improve the diesel component productive rate to strengthen adaptive faculty as far as possible to organic nitrogen compound in the raw material.In order to improve diesel yield, may need to the second reacting part dispensing ammonia.
In second reactive moieties, as required, before the hydrocracking catalyst bed, the Hydrobon catalyst bed can be set.
At the second cold anticyclone separate part, described second reaction effluent cooling also is separated into: second a cold high score gas of mainly being made up of hydrogen, second a cold high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.
The described second cold anticyclone separate part, its separator operation pressure is that the second reactive moieties pressure deducts true pressure and falls, and the difference of the second cold anticyclone separate part working pressure and reactive moieties pressure should not be crossed low or too high, be generally 0.5～1.2MPa, be preferably 0.8MPa.
The service temperature of the second cold anticyclone separate part is generally 30～70 ℃, is preferably 30～60 ℃.
The second cold high score fluid body is isolated diesel oil distillate at the second cold high score fluid body separate part: at this, the described second cold high score oil at first reduces pressure usually, 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, naphtha fraction (or light naphthar and heavy naphtha), diesel oil distillate (or low freezing point diesel fuel and high freezing point diesel fuel) (or solar oil and heavy gas oil) usually and the more double distilled that may the exist product that grades.
The principle of ammonia step and the principle of additional sulphur are washed in the water filling of second reaction effluent, and to wash the ammonia step identical with additional sulphur step with the water filling of first reaction effluent.
The described second cold high score gas 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 described second cold high score gas gas and return second reactive moieties and form circulating hydrogen, so that necessary amounts of hydrogen of second reactive moieties and hydrogen concentration to be provided; In order to improve plant investment efficient, must guarantee that the second recycle hydrogen concentration is not less than aforesaid low limit value, for this reason, distribute according to concrete feedstock property, reaction conditions, product, can get rid of a part described second cold high score gas gas (hereinafter to be referred as the second cold high score gas discharging gas) to get rid of methane, the ethane that reaction produces.Discharge gas for the second cold high score gas, can adopt conventional membrane separation process or pressure swing adsorption technique or oil wash technology to realize hydrogen-non-hydrogen gaseous fraction separation, and the hydrogen that reclaims is used as new hydrogen.
The second new hydrogen (raw hydrogen) enters second reactive moieties to replenish the hydrogen that second reaction process consumes, and the second 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, the second thermal high separate part can be set, in this flow process, second reaction effluent is introduced into service temperature and is generally 150～380 ℃, is preferably 200～280 ℃ the second thermal high separate part and is separated into: second a hot high score gas gas of mainly being made up of hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon group, main second a hot high score fluid body of being made up of conventional liq hydrocarbon and dissolved hydrogen.The second hot high score gas gas enters the second cold anticyclone separate part.The second hot high score fluid body is isolated diesel oil distillate at the second hot high score fluid body separate part (comprise and separate and or fractionated process).The second hot high score fluid body separate part and the second cold high score fluid body separate part can partial commons or all shared.
Metal, oxygen, sulphur, the nitrogen of the typical carbolineum hydrocracking process of the present invention in can effective elimination carbolineum, make wherein saturated, the cracking of at least a portion fused ring compound, oil property is improved significantly, and naphtha fraction can be used as high-quality catalytic reforming raw material component, diesel oil distillate can be used as fine-quality diesel oil blending component.
Hydrocracking reaction one speech of second reactive moieties of the present invention, refer under hydrogen and suitable cracking catalyst existence condition, the cracking reaction process of the consumption hydrogen that the second reactive moieties stock oil takes place, its minimum reaction depth should possess MIN industrial significance: the diesel oil distillate of promptly producing expection character, should be according to the second reactive moieties stock oil character, expection diesel oil distillate character and cracking catalyst performance are determined: general hydrocracking is given birth to olefiant 95% and is distillated a temperature to distillate a temperature than 95% of raw material carbolineum low more than 60 ℃, usually low more than 100 ℃, preferably low more than 125 ℃ (being lower than 365 ℃) such as making hydrocracking give birth to the olefiant conventional boiling temperature of last running, in the hope of improving the diesel oil distillate cetane value, reduce diesel oil distillate density to re-set target, take into account liquid yield simultaneously, (last running is fit to be used as diesel component to simplify the fractionation flow process, save the diesel component and the fractionating step of heavy constituent more) and reduce the process energy consumption significantly (because of diesel component is the maximum product, as have the diesel component and the fractionating step of heavy constituent more, then fractionation energy consumption is huge).
Second to generate the flow process mode of separating of oil part unrestricted, and such as being following mode: entering after the second cold high score oil decompression at pressure is that 0.4～4.0MPa, temperature are the second cold low separator of operating under 30～70 ℃ the condition and are separated into the second cold low separator gas and the second cold low separator liquid; The second cold low separator liquid enters the stabilizer tower system after through heat exchange (reclaim second usually and generate the last running product of separating of oil part and the heat energy of second reaction effluent) and possible heating (using process furnace usually).
Enter at pressure after the second hot high score oil decompression that may exist and be second thermal low-pressure separators of operating under the condition of 0.4～4.0MPa and be separated into the second thermal low-pressure separators gas and the second thermal low-pressure separators liquid; The second thermal low-pressure separators liquid enters described stabilizer tower system.
If naphtha fraction content less (such as being less than 15%) in the stabilizer tower charging of the separating of oil part of second generation, this stabilizer tower can be the stripping operation scheme that adopts logical steam at the bottom of the tower, the stabilizer tower system comprises the trim the top of column system, return tank is discharged and is stablized overhead gas and raw naphtha, and the working pressure of tower is generally 0.15～1.0MPa, is preferably 0.25～0.8MPa; The aqueous last running that the self stabilization tower bottom is discharged enters after the decompression dehydration tower of negative pressure (as pressure-controlling in 0.025～0.05MPa (absolute pressure)) operation down removes water becomes last running.
If naphtha fraction content more (such as more than 15%) in the stabilizer tower charging of the separating of oil part of second generation, this stabilizer tower can be to adopt to establish the operation scheme of bottom reboiler (using process furnace usually), the stabilizer tower system comprises the trim the top of column system, return tank is discharged and is stablized overhead gas and raw naphtha, and the working pressure of tower is generally 0.15～1.0MPa, is preferably 0.3～0.5MPa; The self stabilization tower bottom is discharged last running.
If naphtha fraction content is more in the stabilizer tower charging (such as more than 15%), this stabilizer tower can also be to adopt to establish the operation scheme of bottom reboiler (using process furnace usually), the stabilizer tower system comprises the trim the top of column system, return tank is discharged and is stablized overhead gas and thick light oil (mainly being made up of liquefied gas component and light naphthar component), and the working pressure of tower is generally 1.0～2.0MPa, is preferably 1.2～1.8MPa.The self stabilization tower bottom is discharged mainly oil at the bottom of the stabilizer tower of being made up of petroleum naphtha and last running, usually enter separation column, separation column adopts the operation scheme of establishing bottom reboiler (using process furnace usually) or charging process furnace usually, fractionating column system comprises the trim the top of column system, and the working pressure of tower is generally 0.015～0.8MPa (0.085～0.7MPa gauge pressure), is preferably 0.05～0.25MPa; Oil at the bottom of the separation column of mainly being made up of last running is discharged in the separation column bottom.As required, separation column can be provided with one or more side-cut strippers, and side-cut stripper can adopt water vapor stripping mode or reboiler is set or the reduction vaporization mode is operated.
According to the present invention, the thick light oil (mainly being made up of liquefied gas component and light naphthar component) that stabilizer tower system return tank is discharged can be further separated into narrow fraction product such as petroleum naphtha, liquefied gas etc.
According to the present invention, the hydrocracking high score is separating of oil to be the narrow fraction oil product, and partly or entirely hydrocracking cut product (normally boiling range soprano) is circulated to Hydrobon catalyst bed component part or all " makes with extra care cracking systemic circulation flow process ".
According to the present invention, the hydrocracking high score is separating of oil to be the narrow fraction oil product, and partly or entirely hydrocracking cut product (normally boiling range soprano) is circulated to hydrocracking catalyst bed component part or whole " cracking partial circulating flow process ".
According to the present invention, can increase by the second cold high score oil quantity with being circulated to the second cold anticyclone separate part after the pressurization of the part second light pressure separator liquid, strengthen conventional gas hydrocarbon ability in the second cold high score oil dissolving second cold high score gas, improve the second cold high score gas hydrogen purity.
According to the present invention, can use a kind of hydro carbons hydrogenation process heat recovery method of CN101067095A, generate the oil separation part branch in hydrocracking circulation heat-obtaining oil system is set, reclaim the heat energy of hydrofining intermediate reaction effluent or hydrofining end reaction effluent, or the heat energy of recovery hydrocracking intermediate reaction effluent or hydrocracking end reaction effluent, be used to provide reboiling heat or heats cold logistics at the bottom of the fractionation Tata, but fuel saving consumption reduces the process furnace scale.At this moment, reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, shunting, heat release became the oil circulation use of low temperature heat-obtaining again.
Compare with known carbolineum hydrogenation technique, the invention has the advantages that:
1. can not establish the separating of oil part of hydrofining high score, flow process is greatly simplified, and can significantly reduce construction investment, simplifies the operation, and cuts down the consumption of energy;
2. can not establish the separating of oil part of hydrofining high score, avoid the loss of the hydrogen in the cold high score oil of hydrofining;
When 3. hydrocracking partly is provided with hydrocracking thermal high separate part, can significantly avoid hydrocracking reaction effluent heat-energy losses, cut down the consumption of energy, can significantly reduce running expense;
4. form circulation process flexibly.
Embodiment one
Publication number is the patent application document of CN101033409A, and embodiment is used the inventive method instead, has cancelled first and has generated separating of oil part, and flow process is greatly simplified, and has significantly reduced construction investment, has simplified operation, has reduced energy consumption.
Embodiment two
Compare with the embodiment of the invention one, hydrofining thermal high separate part is set, the hot high score oil of hydrofining enters the hydrocracking catalyst bed, has significantly avoided hydrofining reaction effluent heat-energy losses, has reduced energy consumption.Be equivalent to use a kind of method for hydrogenating coal tar of CN101041783A.
Embodiment three
Compare with the embodiment of the invention one, hydrocracking thermal high separate part is set, the hot high score oil of hydrocracking enters hydrocracking and generates separating of oil part, has significantly avoided hydrocracking reaction effluent heat-energy losses, has reduced energy consumption.
Embodiment four
On the embodiment of the invention two bases, the hydrocracking high score is separating of oil to be narrow fraction oil product such as petroleum naphtha, solar oil, last running (heavy gas oil component and possible wax oil component), and partly or entirely hydrocracking last running product is circulated to Hydrobon catalyst bed component part or all " refining cracking systemic circulation flow processs ".
Embodiment five
On the embodiment of the invention two bases, the hydrocracking high score is separating of oil to be narrow fraction oil product such as petroleum naphtha, solar oil, last running (heavy gas oil component and possible wax oil component), and partly or entirely hydrocracking last running product is circulated to hydrocracking catalyst bed component part or all " cracking partial circulating flow process ".
Embodiment six
On the embodiment of the invention two bases, increase by the second cold high score oil quantity with being circulated to the second cold anticyclone separate part after 50% the second cold low separator liquid pressurization, strengthen conventional gas hydrocarbon ability in the second cold high score oil dissolving second cold high score gas, improve the second cold high score gas hydrogen purity.
Embodiment seven
On the embodiment of the invention two bases, used a kind of hydro carbons hydrogenation process heat recovery method of CN101067095A, generate separating of oil/fractionation in hydrocracking circulation heat-obtaining oil system partly is set, reclaim the heat energy of intermediate reaction effluent or end reaction effluent, be used to provide reboiling heat at the bottom of the fractionation Tata, but fuel saving consumption reduces fractionation part process furnace scale.
Claims (28)
1. hydrocarbon hydrogenating method is characterized in that comprising following steps:
1. in first reactive moieties, under hydrogen and Hydrobon catalyst existence condition, first raw material hydrocarbon is finished hydrofining reaction, generates first reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon;
2. at the first cold anticyclone separate part, first reaction effluent cooling and being separated into after the water filling: first a cold high score gas of mainly forming by hydrogen, a first cold high score oil of mainly forming by conventional gas hydrocarbon, conventional liq hydrocarbon and dissolved hydrogen, first a cold high score water of mainly forming by water, dissolved ammonia and dissolved hydrogen sulfide;
3. at least a portion described first cold high score gas gas returns first reactive moieties;
4. in second reactive moieties, under hydrogen and hydrocracking catalyst existence condition, at least a portion described first cold high score oil is finished hydrocracking reaction, generates second reaction effluent of being made up of hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon;
5. at the second cold anticyclone separate part, described second reaction effluent cooling also is separated into: second a cold high score gas of mainly being made up of hydrogen, second a cold high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.
2. method according to claim 1 is characterized in that:
First raw material hydrocarbon is the hydrocarbon based on carbolineum.
3. method according to claim 1 is characterized in that:
First raw material hydrocarbon is a carbolineum.
4. method according to claim 3 is characterized in that:
The first reactive moieties operational condition is: temperature is that 250～480 ℃, pressure are that 6.0～30.0MPa, catalyst for refining volume space velocity are 0.05～15hr
-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1;
The second reactive moieties operational condition is: in temperature is that 300～480 ℃, pressure are that 6.0～30.0MPa, cracking catalyst volume space velocity are 0.05～15hr
-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.
5. method according to claim 3 is characterized in that:
The first reactive moieties operational condition is: temperature is that 320～415 ℃, pressure are that 10.0～25.0MPa, catalyst for refining volume space velocity are 0.2～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1;
The second reactive moieties operational condition is: 330～440 ℃, pressure are that 10.0～25.0MPa, cracking catalyst volume space velocity are 0.4～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.
6. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: in first reactive moieties, hydrofining gives birth to that olefiant nitrogen content is reduced to that 1500PPm is following, hydrofining gives birth to that olefiant sulphur content is reduced to that 400PPm is following, the first raw material hydrocarbon carbon residue decreasing ratio is greater than 70%.
7. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: in first reactive moieties, hydrofining gives birth to that olefiant nitrogen content is reduced to that 800PPm is following, hydrofining gives birth to that olefiant sulphur content is reduced to that 300PPm is following, the first raw material hydrocarbon carbon residue decreasing ratio is greater than 90%.
8. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: in first reactive moieties, hydrofining gives birth to that olefiant nitrogen content is reduced to that 400PPm is following, hydrofining gives birth to that olefiant sulphur content is reduced to that 200PPm is following, the first raw material hydrocarbon carbon residue decreasing ratio is greater than 95%.
9. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: hydrocracking is given birth to olefiant 95% and is distillated a temperature and distillate a temperature than 95% of first raw material hydrocarbon and hang down more than 60 ℃.
10. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: hydrocracking is given birth to olefiant 95% and is distillated a temperature and distillate a temperature than 95% of first raw material hydrocarbon and hang down more than 100 ℃.
11. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: hydrocracking is given birth to olefiant 95% and is distillated a temperature and distillate a temperature than 95% of first raw material hydrocarbon and hang down more than 125 ℃.
12., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
First reaction effluent enters the first thermal high separate part and is separated into: first a hot high score gas of mainly being made up of hydrogen, first a hot high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.The first hot high score gas enters the first cold anticyclone separate part, and the first hot high score oil enters second reactive moieties and contacts with hydrocracking catalyst.
13., it is characterized in that according to the described method of claim 12:
The first thermal high separate part service temperature is 150～380 ℃.
14., it is characterized in that according to the described method of claim 12:
The first thermal high separate part service temperature is 200～280 ℃.
15., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Second reaction effluent enters the second thermal high separate part and is separated into: second a hot high score gas of mainly being made up of hydrogen, second a hot high score oil of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.The second hot high score gas enters the second cold anticyclone separate part.
16., it is characterized in that according to the described method of claim 15:
The second thermal high separate part service temperature is 150～380 ℃.
17., it is characterized in that according to the described method of claim 15:
The second thermal high separate part service temperature is 200～280 ℃.
18., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Separate second reactive moieties generation oil and obtain the narrow fraction oil product, the narrow fraction oil product that at least a portion boiling range is the highest is circulated to the Hydrobon catalyst bed and does the use of second raw material hydrocarbon.
19., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Separate second reactive moieties generation oil and obtain the narrow fraction oil product, the narrow fraction oil product that at least a portion boiling range is the highest is circulated to the hydrocracking catalyst bed.
20., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Entering after the decompression of second cold high score oil at pressure is that 0.4～4.0MPa, temperature are the second cold low separator of operating under 30～70 ℃ the condition and are separated into the second cold low separator gas and the second cold low separator liquid; The part second cold low separator liquid is circulated to the second cold anticyclone separate part and contacts with gas in second reaction effluent.
21., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Hydrofining reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
22., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Hydrofining intermediate reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
23., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Hydrocracking reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
24., it is characterized in that according to claim 2 or 3 or 4 or 5 described methods:
Hydrocracking intermediate reaction effluent and the heat exchange of low temperature heat-obtaining oil form low-temp reaction effluent and high temperature heat-obtaining oil; High temperature heat-obtaining oil enters the separation column bottom, and after liquid phase stream mixed in the separation column, separation, heat release became the oil circulation use of low temperature heat-obtaining again.
25., it is characterized in that according to the described method of claim 12:
The part first hot high score oil enters first reactive moieties and contacts with Hydrobon catalyst.
26., it is characterized in that according to the described method of claim 13:
The part first hot high score oil enters first reactive moieties and contacts with Hydrobon catalyst.
27., it is characterized in that according to the described method of claim 14:
The part first hot high score oil enters first reactive moieties and contacts with Hydrobon catalyst.
28. according to claim 2 or 3 or 4 or 5 described methods, it is characterized in that: raw material carbolineum is dehydration carbolineum.
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| CN200910174845A CN101712887A (en) | 2009-10-18 | 2009-10-18 | Hydrocarbon hydrogenating method |
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| CN200910174845A CN101712887A (en) | 2009-10-18 | 2009-10-18 | Hydrocarbon hydrogenating method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106318463A (en) * | 2016-08-26 | 2017-01-11 | 山东恒信科技发展有限公司 | Anthracene oil hydrogenation method |
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| WO2000034416A1 (en) * | 1998-12-08 | 2000-06-15 | Exxon Research And Engineering Company | Production of low sulfur/low aromatics distillates |
| CN101024780A (en) * | 2006-02-26 | 2007-08-29 | 何巨堂 | Method for hydrogenation cracking anthracent |
| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
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2009
- 2009-10-18 CN CN200910174845A patent/CN101712887A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000034416A1 (en) * | 1998-12-08 | 2000-06-15 | Exxon Research And Engineering Company | Production of low sulfur/low aromatics distillates |
| CN101024780A (en) * | 2006-02-26 | 2007-08-29 | 何巨堂 | Method for hydrogenation cracking anthracent |
| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
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