CN102146298A - Hydrocarbon hydrogenation conversion process combined method - Google Patents

Hydrocarbon hydrogenation conversion process combined method Download PDF

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CN102146298A
CN102146298A CN2011100467481A CN201110046748A CN102146298A CN 102146298 A CN102146298 A CN 102146298A CN 2011100467481 A CN2011100467481 A CN 2011100467481A CN 201110046748 A CN201110046748 A CN 201110046748A CN 102146298 A CN102146298 A CN 102146298A
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hydrogen
hydrocarbon
reactive moieties
raw material
cold anticyclone
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何巨堂
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Abstract

The invention relates to a hydrocarbon hydrogenation conversion process combined method which comprises steps as follows: a first reaction effluent E1 obtained by new hydrogen FH and a first hydrocarbon raw material F1 at a first reaction part R1 is separated into a first cold high-pressure hydrogen-rich gas V1 and a first cold high-pressure hydrocarbon liquid L1 at a first cold high-pressure separation part S1; at least part of V1 enters a second reaction part R2 for treating a second hydrocarbon raw material F2; and a second reaction effluent E2 is separated into a second cold high-pressure hydrogen-rich gas V2 and a second cold high-pressure hydrocarbon liquid L2 at a second cold high-pressure separation part S2. The invention also comprises the step of recovering dissolved hydrogen in the L2. The invention has obvious effects of saving the step of high-pressure operation, reducing the hydrogen consumption and the like, is suitable for the combination of a medium/low-pressure low-hydrogen-consumption hydrocarbon hydrogenation process (such as petroleum-based gasoline/diesel hydrofining, wax oil hydrodesulfurization or low-sulfur diesel hydrogenation and aroma removal process) and a high-pressure high-hydrogen-consumption hydrocarbon hydrogenation process (such as coal tar hydrogenation process).

Description

A kind of hydrocarbon hydroconversion process combined method
Technical field
The present invention relates to a kind of hydrocarbon hydroconversion process combined method; Say especially and the present invention relates to the combined method that a kind of reaction process hydrogen consumption differs bigger hydrocarbon hydroconversion process; More particularly the present invention relates to the combined method of a kind of petroleum base hydrocarbon unifining process and coal-tar base hydrocarbon hydroconversion process.
Background technology
As everyone knows, the hydrocarbon hydroconversion process is the conversion process of the consumption hydrogen of hydrocarbon feed under the hydrogen existence condition, described hydrocarbon raw material can be the hydro carbons from oil or oil shale or oil-sand or coal, the cut scope of raw material hydrocarbon from gasoline, kerosene, diesel oil, wax oil up to residual oil, in most cases above-mentioned raw materials contains assorted element such as oxygen, sulphur and nitrogen etc., and coal tar then contains a large amount of assorted elements and the assorted element of considerable part and carbon atom and constitutes ring texture.
In hydroconversion process, under the hydrogen existence condition, hydrocarbon raw material contacts with a kind of or two kinds or multiple catalyzer in one or two or more reactors, and it is that 250～530 ℃, pressure are 1.4～28.0MPa that reaction conditions is generally temperature.The reaction pressure of common described low-voltage hydrogenation, medium-pressure hydrocracking, high-pressure hydrogenation correspondence is that 4.0MPa is following, 4.0～13.5MPa, more than the 13.5MPa.The typical chemical reaction that hydroconversion process takes place comprises that hydrodemetallation (HDM), hydrogenating desulfurization, hydrogenation alkene are saturated, hydrodenitrification, aromatic hydrogenation are saturated, hydrocracking and hydroisomerization, and some reactions belong to the secondary reaction of a product.Hydroconversion reactions part effluent contains unreacted hydrogen, conversion and unconverted hydro carbons and gas products, and these gas products comprise normally gaseous hydrocarbon and foreign gas such as H 2S, NH 3, H 2O.Usually, the hydroconversion process reaction effluent is separated into the hydrogen-rich gas and the hydrocarbon liquid that are circulated to reactive moieties and generates oil, common described hydrocarbon liquid generates the oily narrow fraction that obtains through fractionation and can be used as product or other hydroconversion process raw material or catalytically cracked material, especially, in hydrocracking process, it can be narrow fraction liquid product such as light naphthar, heavy naphtha, boat coal, diesel oil and hydrocracking tail oil by fractionation that described hydrocarbon liquid generates oil, can return some narrow fraction oil to reactive moieties.The initially-separate of described reaction effluent normally adopts " cold minute flow process " to finish.In cold minute flow process, reaction effluent is cooled to suitable temperature (being generally 25～65 ℃), is separated into then that hydrocarbon liquid generates oil and its hydrogen concentration is enough to be circulated to the hydrogen-rich gas that reactive moieties is used.Flow process can obtain maximum hydrogen recovery rate and raising recycle hydrogen hydrogen concentration by reducing oily ability and the oily receptivity to hydrogen of reduction generation that absorbs the conventional gas hydrocarbon of separation temperature enhancing generation in cold minute, but a considerable amount of heat energy in the loss reaction effluent still have a certain amount of dissolved hydrogen hydrogen loss simultaneously.The another kind of method of finishing the initially-separate of reaction effluent is " a thermoanalysis journey ", it can improve reaction effluent heat energy utilization rate, reduces the reaction effluent cooling load and reduce the cooling heat exchanger area, but, because reaction effluent contains more dissolved hydrogen in the hydrocarbon liquid that high pressure hot separator is discharged, it can increase hydrogen loss, because the hydrocarbon liquid quantity that cold high pressure separator is discharged reduces, it can reduce the recycle hydrogen hydrogen concentration and increase hydrogen loss.Simultaneously, the thermal high that high pressure hot separator is discharged separates gas and is cooled to certain low temperature and enters cold high pressure separator and finish gas-liquid separation to obtain the process of circulating hydrogen, still has the investment of a considerable amount of heat-energy losses and corresponding cooling equipment inevitably.
This section is described petroleum base hydrocarbon hydroconversion process.The petroleum base hydro carbons refers to from crude oil or crude oil time processing (such as crude distillation) or crude oil secondary processing (such as catalytic cracking, the coking thermally splitting of crude distillation cut) gained hydro carbons.The petroleum base hydrocarbon hydrogenating conversion process is being classified as hydrotreatment process, unifining process and hydrocracking process traditionally, though there is no significant line of delimitation between these three kinds of hydroconversion process, there are well-known difference in the depth of conversion of raw material and raw material hydrocarbon unit's hydrogen consumption.The hydrotreatment process is that demulcent is a kind of in above-mentioned three class processes, and its raw material hydrocarbon unit weight hydrogen consumption is minimum usually, and its numerical value is between 0.01～0.50%.The application of unifining process is more extensive than the hydrotreatment process, and also comprised the hydrotreatment process in a broad sense, hydrogenating desulfurization, hydrodenitrification and hydrogenation aromatic hydrocarbons that typical unifining process comprises hydrocarbon raw material are saturated, the wax oil hydrogenation desulfurization is a kind of important unifining process, usually unifining process raw material hydrocarbon unit hydrogen consumption is higher than the raw material hydrocarbon unit weight hydrogen consumption of hydrotreatment process process, and its numerical value is between 0.5～1.5%.Hydrocracking process be in above-mentioned three class processes hydrocarbon raw material by maximum a kind of of cracked, it is a raw material with gasoline, kerosene, diesel oil, wax oil and residual oil, be widely used in production liquefied petroleum gas (LPG), catalytic reforming raw material, high-quality intermediate oil, cracking ethylene raw material, WHITE OIL PRODUCTION raw material and lubricated wet goods, usually its raw material hydrocarbon unit's hydrogen consumption is higher than unifining process raw material hydrocarbon unit hydrogen consumption, and its numerical value is between 1.3～3%.Hydrogen to oil volume ratio is an important operating parameters, because petroleum base fraction oil hydrogenation refining process hydrogen consumption is little, thermal discharge is less, the thermophore recycle hydrogen quantity that is mainly used in the temperature rise of control bed is less, and promptly hydrogen to oil volume ratio is lower usually.With the petroleum base diesel oil hydrofining is example, and between 300～600, raw material hydrocarbon unit's hydrogen consumption numerical value calculates by 1.35% usually, and global cycle hydrogen amount approximately is 2～4 times of new hydrogen amount.
This section is described coal-tar base hydrocarbon hydroconversion process.The coal-tar base hydro carbons refers to from coal tar or coal tar time processing (such as coal tar distillation) or coal tar secondary processing (such as visbreaking thermally splitting, the coking thermally splitting of coal-tar pitch) gained hydro carbons.The coal-tar base hydrocarbon hydrogenating conversion process comprises coal tar hydrogenation modification process and coal tar hydrocracking process, and the depth of conversion of raw material and raw material hydrocarbon unit's hydrogen consumption have well-known difference.This paper does not use the reason of " coal tar hydrorefining process " saying to be: coal tar contains a large amount of assorted elements and considerable part is positioned on the loop chain, a large amount of " removing assorted element reaction " that " coal tar hydrorefining process " takes place itself is exactly " chain rupture or ring-opening reaction ", promptly there be " the hydrofining cracking effect of coal tar ", very easily cause the chaos of conception.Hydrogenation deoxidation, the hydrogenation alkene that typical coal tar hydrogenation modification process comprises hydrocarbon raw material is saturated, hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification and aromatic hydrocarbons are saturated, and its raw material hydrocarbon unit's hydrogen consumption numerical value is between 2.5～7.0%.Coalite tar distillate hydrogenation upgrading process hydrocarbon unit hydrogen consumption numerical value is usually between 2.5～3.5%, between 3.5～4.5%, coal-tar heavy oil carbolineum hydro-upgrading process hydrocarbon unit hydrogen consumption numerical value is usually between 5.5～7.0% usually for coal-tar middle oil distillate hydrogenation upgrading process hydrocarbon unit hydrogen consumption numerical value.The coal tar hydrocracking process is based on the hydro-upgrading process, further comprises that hydro-upgrading generates " upgrading+cracking " process that oily macromole hydrocarbon is converted into micromolecular cracking process that its raw material hydrocarbon unit's hydrogen consumption numerical value is between 3.5～9.5%.
For hydrocarbon hydrogenation process, hydrogen richness is an essential property of hydrocarbon feed, this numerical value changes within the specific limits, the hydrogen richness of paraffin-base petroleum cut can be up to more than 14% (weight), and the hydrogen richness of dead oil can be lower than 6% (weight), this also directly points out: must add a large amount of hydrogen with the dead oil process of producing oil fuel products substitution product and promptly have the huge new hydrogen logistics of quantity, clearly, the hydrogenating materials oil of same weight, the hydrogen consumption of coal tar hydrogenating process is 3～5 times of petroleum base fraction oil hydrogenation refining process hydrogen consumption even more, even can reach the new hydrogen quantity of petroleum base fraction oil hydrogenation refining process need and the summation of recycle hydrogen quantity.And core purpose of the present invention be utilize the quantity of such new hydrogen logistics big, the characteristics of purity high impurity such as () no hydrogen sulfide, form hydrocarbon hydroconversion process combination process.
When factory builds low hydrogen consumption hydrocarbon hydrocracking device (such as petroleum base distillate medium-pressure hydrocracking refining plant) and high hydrogen consumption hydrocracking device (such as coal-tar base distillate high-pressure hydrogenation conversion system) simultaneously, will face following situation according to prior art: because two kinds of pressure processes differ usually very big, therefore, from reducing the investment angle, should establish two reactive systems, select for use suitable separately reaction pressure to finish the hydrogenation reaction of expection, invest bigger but build two covering devices.The present invention proposes a kind of reaction process hydrogen consumption and differs the combined method that big, reaction pressure differs bigger hydrocarbon hydroconversion process, addresses the above problem.
Have multiple about the combination process that contains two or more hydroconversion process, as method as described in US 2671754, US 3026260, US 3365388, US 3592758, US 3655551, the US 5026472, its common trait is that the hydrocarbon liquid product of upstream reaction zone effluent sepn process gained carries out the secondary hydrocracking as downstream reaction district hydrocarbon feed.Chinese patent CN 10169668 relates to a kind of logistics that will contain heavy hydrocarbon under the hydrogen existence condition and is transformed into the method that contains the low boiling point hydrocarbon logistics, the main conversion fluid stream of its first conversion zone raw material, first section effluent is separated into air-flow and liquid stream at separate part, air-flow enters second conversion zone, and second conversion zone mainly transforms hydro carbons in the air-flow.The Chinese patent ZL patent No. 99103876.2 relates to a kind of converting and combining method for hydrogenation of hydrocarbon, and its core feature is: the thermal high of first reaction effluent separates gas dependence self pressure and enters second reactive moieties, saves the special-purpose recycle hydrogen flow of second reactive moieties.Above patent does not all relate to the combined method of the hydrocarbon hydroconversion process that working pressure difference is big, the hydrogen consumption differs greatly.
Technical solution of the present invention is not appeared in the newspapers.
The objective of the invention is to propose a kind of combined method, working pressure difference is big, that the hydrogen consumption differs greatly hydrocarbon hydroconversion process makes up, and has the effect that reduces the high top pressure operation step, reduces the dissolved hydrogen loss.
Summary of the invention
The high aromatic hydrocarbons intermediate oil of the high nitrogen of a kind of two-stage method of the present invention hydrogenating conversion process is characterized in that comprising following steps:
1. at the first reactive moieties R1, the new hydrogen FH and the first hydrocarbon raw material F1 generate first a reaction effluent E1 who contains components such as hydrogen, hydro carbons through hydroconversion reactions;
2. the first reaction effluent E1 finishes a cold anticyclone sepn process at the first cold anticyclone separate part S1, generates the first cold anticyclone hydrogen-rich gas V1 and first a cold anticyclone hydrocarbon liquid L1 who contains most of conventional liq hydrocarbon component among the first reaction effluent E1 who contains most of hydrogen among the first reaction effluent E1, most of conventional gas hydrocarbon component and small part conventional liq hydrocarbon component;
3. the described first cold anticyclone hydrogen-rich gas V1 of at least a portion is imported the 4. described second reactive moieties R2 of step;
4. at the second reactive moieties R2, the second hydrocarbon raw material F2 generates second a reaction effluent E2 who contains components such as hydrogen, hydro carbons through hydroconversion reactions under the hydrogen existence condition;
5. the second reaction effluent E2 finishes a cold anticyclone sepn process at the second cold anticyclone separate part S2, generate one contain most of hydrogen among the second reaction effluent E2, most of conventional gas hydrocarbon component and small part conventional liq hydrocarbon component the second cold anticyclone hydrogen-rich gas V2 and second a cold anticyclone hydrocarbon liquid L2 who contains most of conventional liq hydrocarbon component among the second reaction effluent E2.
The common recycle second cold anticyclone hydrogen-rich gas V2, the described second cold anticyclone hydrogen-rich gas V2 of at least a portion (most of to whole) returns the second reactive moieties R2 and recycles.
In order to discharge non-hydrogen components in the second cold anticyclone hydrogen-rich gas V2, a part of second cold anticyclone hydrogen-rich gas V2 puies forward dense part through membrane sepn hydrogen and obtains one and carry dense hydrogen and return and return the second reactive moieties R2 and recycle.
The hydrogen volume concentration of the described second cold anticyclone hydrogen-rich gas V2 is not less than 70% usually, generally is not less than 75%, preferably is higher than 80%.
In order to give full play to effect of the present invention: the common second hydrocarbon raw material F2 at the unit weight hydrogen consumption of the second reactive moieties R2 and the first hydrocarbon raw material F1 at the ratio of the unit weight hydrogen consumption of the first reactive moieties R1 greater than 2.0.
The working pressure of the described second reactive moieties R2 is higher than the difference of the working pressure of the first reactive moieties R1: be not less than 3.0MPa usually, generally be not less than 5.0MPa.
Usually, the first hydrocarbon raw material F1 is 100～550 ℃ of petroleum base hydrocarbon compositions by conventional boiling spread mainly, and the second hydrocarbon raw material F2 is 100～530 ℃ of coal-tar base hydrocarbon compositions by conventional boiling spread mainly.
The catalyzer of the described first reactive moieties R1 can be the deeply de-aromatizing noble metal catalyst of anti-sulphur not.
The operational condition of each step of the present invention is generally:
1. the service temperature of the first reactive moieties R1 is 250～480 ℃, and working pressure is 3.5～20.0MPa;
2. the service temperature of the first cold anticyclone separate part S1 is below 100 ℃; The special-purpose circulating hydrogen compressor of first reactive moieties is not set;
4. the service temperature of the second reactive moieties R2 is 250～480 ℃, and working pressure is 3.5～28.0MPa;
5. the service temperature of the second cold anticyclone separate part S2 is below 100 ℃.
The operational condition of each step of the present invention is generally:
1. the service temperature of the first reactive moieties R1 is 300～440 ℃, and working pressure is 3.5～15.0MPa;
2. the first cold anticyclone separate part S1 service temperature is 30～65 ℃; The special-purpose circulating hydrogen compressor of first reactive moieties is not set;
4. the service temperature of the second reactive moieties R2 is 300～440 ℃, and working pressure is 8.0～25.0MPa;
5. the service temperature of the second cold anticyclone separate part S2 is 30～65 ℃.
The step that the present invention reclaims dissolved hydrogen among the second cold anticyclone hydrocarbon liquid L2 is as follows:
At the 4th separate part S4, by reducing by the second cold anticyclone hydrocarbon liquid L2 pressure, flash distillation forms the 4th gas V4 and the 4th hydrocarbon liquid L4 who mainly is made up of hydrocarbon component that mainly are made up of hydrogen on volumetric concentration; At least a portion the 4th gas V4 is delivered to the first cold anticyclone separate part to be contacted with the first reaction effluent E1.The hydrogen volume concentration of the 4th gas V4 is not less than 70% usually, generally is not less than 80%.
The present invention is particularly suitable for the combination of petroleum base fraction oil hydrogenation refining process and coal-tar base distillate hydrogenation conversion process, and the operational condition of each step is generally:
1. the first raw material hydrocarbon F1 is the petroleum base distillate, and the operational condition of the first reactive moieties R1 is: temperature is 250 ℃～480 ℃, and pressure is 3.5～20.0MPa, and the hydrogenation catalyst volume space velocity is 0.05～15hr -1, hydrogen/stock oil volume ratio is 400: 1～2000: 1; The first hydrocarbon raw material F1 in the unit weight hydrogen consumption of the first reactive moieties R1 less than 2%;
2. the service temperature of the first cold anticyclone separate part S1 is below 100 ℃; The special-purpose circulating hydrogen compressor of first reactive moieties is not set;
4. the second raw material hydrocarbon F2 is the coal-tar base distillate, and the operational condition of the second reactive moieties R2 is: temperature is 250～480 ℃, and pressure is 8.0～25.0MPa; The hydrogenation catalyst volume space velocity is 0.05～15hr -1, hydrogen/stock oil volume ratio is 400: 1～4000: 1; The second hydrocarbon raw material F2 in the unit weight hydrogen consumption of the second reactive moieties R2 greater than 3%; The working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 3.0MPa at least;
5. the service temperature of the second cold anticyclone separate part S2 is below 100 ℃.
The present invention is particularly suitable for the combination of petroleum base fraction oil hydrogenation refining process and coal-tar base distillate hydrogenation conversion process, and the operational condition of each step is generally:
1. the petroleum base distillate first hydrocarbon raw material F1 in the unit weight hydrogen consumption of the first reactive moieties R2 less than 1.5%;
2. the service temperature of the first cold anticyclone separate part S1 is 35～60 ℃;
4. the coal-tar base distillate second hydrocarbon raw material F2 in the unit weight hydrogen consumption of the second reactive moieties R2 greater than 4.5%; The working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 5.0MPa at least;
5. the service temperature of the second cold anticyclone separate part S2 is 35～60 ℃.
The present invention is particularly suitable for the combination of petroleum base fraction oil hydrogenation refining process and coal-tar base distillate hydrogenation conversion process, and the operational condition of each step is preferably:
1. the petroleum base distillate first hydrocarbon raw material F1 in the unit weight hydrogen consumption of the first reactive moieties R2 less than 1.3%;
2. the service temperature of the first cold anticyclone separate part S1 is 40～55 ℃;
4. the coal-tar base distillate second hydrocarbon raw material F2 in the unit weight hydrogen consumption of the second reactive moieties R2 greater than 5.5%; The working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 7.0MPa at least;
5. the service temperature of the second cold anticyclone separate part S2 is 40～55 ℃.
The present invention can constitute the secondary hydrogenation technique: 1. the first hydrocarbon raw material F1 is the fractionation portioned product of the second reaction effluent E2.
The present invention can constitute coal-tar base distillate hydrogenation upgrading process and the upgrading diesel oil deep takes off fragrant secondary hydrogenation technique:
1. the first hydrocarbon raw material F1 is the fractionation portioned product of the second reaction effluent E2, and the first hydrocarbon raw material F1 mainly is made of low-sulfur, low nitrogen diesel component, and the catalyzer of the first reactive moieties R1 is the deeply de-aromatizing noble metal catalyst of not anti-sulphur.
4. the second hydrocarbon raw material F2 is the coal-tar base distillate.
The present invention can constitute the two-stage tandem hydrogenation technique of the first hydrocarbon raw material F1:
1. the 3rd hydrocarbon raw material F3 is the fractionation portioned product of the first reaction effluent E1.
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.
Impurity composition of the present invention refers to the hydride of non-hydrocarbon component in the stock oil such as water, ammonia, hydrogen sulfide, hydrogenchloride etc.
The composition of component of the present invention or concentration or content or yield value unless stated otherwise, are the weight basis value.
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 180 ℃ conventional liq hydrocarbon.
It is 180～355 ℃ hydro carbons that diesel component of the present invention refers to conventional boiling point.
It is 355～530 ℃ hydro carbons that wax oil component of the present invention refers to conventional boiling point.
Two-stage method hydrocarbon oil hydrogenation conversion process of the present invention refers to hydrotreatment process that raw material hydrocarbon is converted into the finished product and comprises two hydrogenation reaction systems (one-stage hydrogenation reactive system and secondary hydrogenation reactive system) and supporting hydrogenated oil separate part (secondary hydrogenation generates separating of oil part and the one-stage hydrogenation that may exist generates separating of oil part).Two hydrogenation reaction systems form overall serial flow on the stock oil flow process.
The hydrogenated oil separate part is separated into the narrow fraction oil product with hydrogenated oil, uses equipment such as separation column usually.
Describe the present invention in detail below in conjunction with accompanying drawing.
Accompanying drawing 1 is first kind of scheme schema of the present invention; Accompanying drawing 2 is second kind of scheme schema of the present invention.
Accompanying drawing is drawn for the present invention is described, but can not limit range of application of the present invention.
First kind of scheme of the present invention as shown in Figure 1, the first hydrocarbon raw material F1 that comes along pipeline 1 with along pipeline 2 and the new hydrogen logistics FH that comes enters the first reactive moieties R1, under certain effectively operating condition, finish first hydroconversion reactions, generate first a reaction effluent E1 who contains hydrogen, hydrocarbon component and possible foreign gas; The first reaction effluent E1 enters the first cold anticyclone separating part S1 along pipeline 4 and finishes a cold anticyclone separation process, generates the first cold anticyclone hydrocarbon liquid L1 that first a cold anticyclone hydrogen-rich gas V1 who contains the conventional liquid hydrocarbon of most of hydrogen, foreign gas and normally gaseous hydrocarbon and small part among the first reaction effluent E1 and are contained most of conventional liquid hydrocarbon and dissolved hydrogen among the first reaction effluent E1; The first cold anticyclone hydrogen-rich gas V1 leaves the first cold anticyclone separating part S1 along pipeline 6, and the described first cold anticyclone hydrogen-rich gas V1 of at least a portion imports the described second reactive moieties R2; Shown in the figure is the situation that whole first cold anticyclone hydrogen-rich gas V1 import the second reactive moieties R2. The second hydrocarbon raw material F2 that comes along pipeline 7 with along pipeline 6 and the high pressure hydrogen-rich gas V1 that comes and may with along pipeline 8 and other hydrogen-rich gas that comes enters the second reactive moieties R2, under certain effectively operating condition, finish second hydroconversion reactions, generate second a reaction effluent E2 who contains hydrogen, foreign gas and hydrocarbon component; The second reaction effluent E2 enters cold anticyclone separating part S2 along pipeline 12 and finishes a cold anticyclone separation process, usually generates the second cold anticyclone hydrocarbon liquid L2 that second a cold anticyclone hydrogen-rich gas V2 who contains most of hydrogen, foreign gas and normally gaseous hydrocarbon and the conventional liquid hydrocarbon of small part among the second reaction effluent E2 and are contained most of conventional liquid hydrocarbon and dissolved hydrogen among the second reaction effluent E2 by reducing by the second reaction effluent E2 temperature; The second cold anticyclone hydrogen-rich gas V2 leaves cold anticyclone separating part S2 along pipeline 14, and the second cold anticyclone hydrocarbon liquid L2 leaves cold anticyclone separating part S2 along pipeline 30.
Combined method of the present invention shown in the accompanying drawing 2 is compared with accompanying drawing 1 and is further characterized in that: the second cold anticyclone hydrogen-rich gas V2 leaves cold anticyclone separating part S2 along pipeline 14, the described second cold anticyclone hydrogen-rich gas V2 of at least a portion returns the second reactive moieties R2 and/or the first reactive moieties R1, and shown in the figure is the situation that the second cold anticyclone hydrogen-rich gas V2 all returns. Returning reactive moieties according to accompanying drawing 2, the second cold anticyclone hydrogen-rich gas V2 before may be through taking off H2S part 15 is taken off H2S processes to form and takes off H2The cold anticyclone hydrogen-rich gas of S, after the circulating hydrogen compressor supercharging, remove the second reactive moieties R2 as recycle hydrogen along pipe 8 along pipe 16, part recycle hydrogen mixes with the new hydrogen that comes along pipe 20 through the concentrate hydrogen that the film separating part obtains along pipe 17, and gaseous mixture enters the first reactive moieties R1 along pipe 2. Recycle hydrogen also can all enter the second reactive moieties R2 in the pipe 16, and shown in the accompanying drawing 2 is that recycle hydrogen enters the first reactive moieties R1 and the second reactive moieties R2 simultaneously in the pipe 16. The new hydrogen that the present invention uses according to accompanying drawing 2, removes the first reactive moieties R1 along pipe 20 after the make-up hydrogen compressor supercharging.
Further, finish second a cold anticyclone hydrocarbon liquid L2 cold low flash process at cold low separating part S4: the cold anticyclone hydrocarbon liquid L3 that leaves cold anticyclone separating part S2 along pipe 30 reduces pressure, flash distillation forms the cold low gas V4 and the cold low hydrocarbon liquid L4 who mainly is made up of hydrocarbon component that mainly are made up of H2, normally gaseous hydrocarbon, cold low gas V4 leaves cold low separating part S4 along pipe 32, and cold low hydrocarbon liquid L4 leaves cold low separating part S4 along pipe 33. The 33 cold low hydrocarbon liquid L4 that leave the second cold low separating part S4 finish a cold low separation process at cold low separating part S5 along pipe, by reducing cold low hydrogen-rich gas V5 and cold low hydrocarbon liquid L5 who on volumetric concentration, is mainly formed by H2 of cold low hydrocarbon liquid L4 pressure initiation, cold low hydrogen-rich gas V5 leaves cold low separating part S5 along pipe 35, and cold low hydrocarbon liquid L5 leaves cold low separating part S5 along pipe 36; At least a portion cold low hydrogen-rich gas V4 is delivered to the first reactive moieties R1 or second reactive moieties R2 use, but be to return the second reactive moieties R2 to use in essence.
Further, leave the first cold anticyclone hydrocarbon liquid L1 of the first cold anticyclone separating part S1 along pipe 23, finish a cold low separation process at cold low separating part S3: by reducing by the first cold anticyclone hydrocarbon liquid L1 pressure, flash distillation forms the cold low hydrogen-rich gas V3 and the cold low hydrocarbon liquid L3 who mainly is made up of hydrocarbon component that mainly are made up of H2 on volumetric concentration, cold low gas V3 leaves cold low separating part S3 along pipe 26, and cold low hydrocarbon liquid L3 leaves cold low separating part S3 along pipe 25.
As required, use compressor in pipeline 2, pipeline 6 systems.
" hydrocarbon hydroconversion process " word refers to hydrocarbon raw material is converted into the desired product hydro carbons under the condition that consumes hydrogen process herein, and described hydroconversion process comprises common described hydrotreatment process, unifining process and hydrocracking process. The hydroconversion process reaction effluent generally includes hydrogen, normally gaseous hydrocarbon, conventional liquid hydrocarbon and foreign gas.
" unifining process " described herein word refers to its raw material weight conversion ratio and is not more than 25% hydroconversion process. Generally described " unifining process " word refers to its raw material weight conversion ratio and is not more than 15% hydroconversion process, and described " unifining process " word refers to its raw material weight conversion ratio and is not more than 10% hydroconversion process especially.
Owing to contain a large amount of sulphur, nitrogen, oxygen, metal etc. in the coal tar, it is to remove sulphur, nitrogen, oxygen, metal as the subtractive process generation of target a large amount of " cracking reaction that the imurity-removal element forms ", although its mechanism is different from the leading reaction (such as the long-chain fracture) of the hydrocracking process of petroleum base wax oil, yet on effect, will be difficult to distinguish, therefore in order to prevent the chaos of conception, this paper is divided into coal tar hydrogenation modification process and coal tar hydrocracking process with the coal-tar base hydrocarbon hydrogenating conversion process.
" foreign gas " of the present invention word refers to the non-hydrocarbon gas that produces that is contained in the reaction effluent in course of reaction, such as H2S and/or the such gas of NH3 of organic sulfur in the hydrocarbon raw material and/or the generation of organic nitrogen hydro-conversion.
" conventional boiling point " described herein word refers to the boiling temperature of material under atmospheric pressure conditions, unless especially dated, boiling point described herein refers to conventional boiling temperature. Can measure its boiling temperature with the ASTM-D86 method for gasoline and lighter hydro carbons, can test its boiling temperature with the ASTM-D1160 method for heavy gas oil and heavier charging. Gasoline boiling point boiling range is about 80～210 ℃, the conventional boiling point boiling range of light gas oil is about 150～350 ℃, and heavy oil is conventional boiling point boiling range be about 350～540 ℃ gas oil and boiling point at the residual oil more than 350 ℃ and boiling point at the decompression residuum more than 550 ℃, unless especially dated, the boiling point boiling range refers to the conventional boiling temperature scope from 5% cut point to 95% cut point.
" the first hydro-conversion part " word refers to herein, comprise the first reactive moieties R1 and the first cold anticyclone separating part S1 and the separating step S3 that may use in interior process.
" the second hydro-conversion part " word refers to herein, comprise the second reactive moieties R2, the second cold anticyclone separating part S2 and separating step S4, the S5 that may use in interior process.
Need to prove that the use of " the first hydro-conversion part ", " the second hydro-conversion part " word does not consist of any restriction to actual content of the present invention just in order to say something.
The first hydrocarbon feed F1 of process of the present invention can be the hydro carbons from oil or coal or oil bearing rock page or leaf or tar sand or coal tar wet goods any appropriate. The first hydrocarbon raw material F1 can be mainly by boiling spread be 50～550 ℃ of hydrocarbon compositions, in particular mainly by 300～530 ℃ hydrocarbon composition. More particularly, the first hydrocarbon feed F1 be the hydro carbons that obtains of the fractional distillation process from the second reaction effluent E2 such as low-sulfur, low nitrogen, contain the diesel oil distillate than polyaromatic, at this moment, the first hydrocarbon feed F1 is the recycle stream that is present between " the first hydro-conversion part " and " the second hydro-conversion part " from the second hydrocarbon raw material F2.
The second hydrocarbon feed F2 of process of the present invention can be the hydro carbons from oil or coal or oil bearing rock page or leaf or tar sand or coal tar wet goods any appropriate. It is 50～550 ℃ of hydrocarbon compositions by boiling spread mainly that the second hydrocarbon raw material F2 can be, and the second hydrocarbon raw material F2 mainly is made up of the hydrocarbon of 60 ℃～550 ℃ of boiling points, and main coal tar or dead oil by 100～500 ℃ forms especially. More particularly, second reactive moieties is united processing the 3rd hydrocarbon feed F3, the 3rd hydrocarbon feed F3 for the high-boiling hydrocarbon that obtains from the fractional distillation process of the first reaction effluent E1 such as hypoxemia, low-sulfur, low nitrogen wax oil, that is to say, the 3rd hydrocarbon feed F3 is from the first hydrocarbon raw material F1, has an oil product work flow of connecting between " the first hydro-conversion part " and " the second hydro-conversion part ".
To specific hydrocracking anabolic process, the actually operating condition of its first reactive moieties R1 depends on the condition as feed composition and process unit process function, changes with the character of the reaction depth of raw material properties, expection and the catalyzer that may use.The first reactive moieties R1 hydrocracking operational condition comprise from as the required mitigation condition of the unifining process that removes a part of sulphur the light charging such as petroleum naphtha or light gas oil until as the hydrogenating desulfurization of high content of wax VACUUM TOWER BOTTOM material or the severe condition of middle pressure hydrocracking process, wherein comprise the coal tar hydrogenating conversion condition of low hydrogen consumption.Demulcent hydrofining condition is: pressure is lower than 3.5MPa, temperature and is lower than 400 ℃, liquid hourly space velocity and is higher than 1.0h -1, hydrogen to oil volume ratio is 35～350, stock oil unit weight hydrogen consumption 0.05～0.5%; Harsh hydrocracking condition comprises: pressure is that 14.0～28.0MPa, temperature are that 400～480 ℃, liquid hourly space velocity are 0.2～0.6h -1, hydrogen to oil volume ratio is 1200～3600, stock oil unit weight hydrogen consumption 2.0～3.0%; Moderate hydrocracking condition and range is: the pressure of 3.5～14.0MPa, and 250～460 ℃ temperature, 0.4～2h-1 liquid hourly space velocity, hydrogen to oil volume ratio are 400～1500, stock oil unit weight hydrogen consumption 0.5～2.0%.The working pressure of the hydroconversion process of combined method of the present invention recommends to be higher than 2.5MPa.
To specific hydrocracking anabolic process, the actually operating condition of its second reactive moieties R2 depends on the condition as feed composition and process unit process function, changes with the character of the reaction depth of raw material properties, expection and the catalyzer that may use.The second reactive moieties R2 hydrocracking operational condition comprises the severe condition of the required mitigation condition of the unifining process that removes a part of sulphur from chargings such as high consumption hydrogen raw material such as coalite tar, coal-tar middle oil, carbolineum, big flow petroleum base wax oil until hydrogenating desulfurization or middle pressure hydrocracking or hydro-upgrading process, wherein comprises the coal tar hydrogenating conversion condition.Coalite tar hydro-upgrading condition is: the pressure of 8.0～12.0MPa, 250～460 ℃ temperature, 0.4～0.8h -1Liquid hourly space velocity, hydrogen to oil volume ratio are 800～1200, stock oil unit weight hydrogen consumption 2.5～3.5%.Coal-tar middle oil hydro-upgrading condition is: the pressure of 15.0～20.0MPa, 300～460 ℃ temperature, 0.3～0.5h -1Liquid hourly space velocity, hydrogen to oil volume ratio are 1800～3000, stock oil unit weight hydrogen consumption 3.5～4.5%.Coal-tar heavy oil carbolineum hydro-upgrading condition is: the pressure of 15.0～25.0MPa, 330～460 ℃ temperature, 0.2～0.4h -1Liquid hourly space velocity, hydrogen to oil volume ratio are 2000～4000, stock oil unit weight hydrogen consumption 5.5～7.5%.If coal tar adopts hydro-upgrading and the processing of hydrocracking two-stage process, then stock oil unit weight hydrogen consumption further improves such as improving 1.0～2.0%.
Disclosed hydrogenation conversion catalyst has multiple, and some appropriate catalyst wherein can be bought from manufacturers.The first reactive moieties R1, the second reactive moieties R2 catalyst system therefor should form and expection process goal and selecting according to raw material, and therefore, the composition variation range of catalyzer is very wide.Typical catalyst is made up of (support) one or more metal components on the inorganics refractory support that distribute, and the metal component on the catalyzer is from the VIII in the periodic table of elements, V and VI family.Selected normally Ni, Co, Mo, Cr and W also contain Fe and Pt sometimes, and the form of the metal on the catalyzer can be metallic element or metal oxide or metallic sulfide or other compound.Every kind of metal content is 0.1～40wt% of catalyzer total amount normally, although the content of metal exceeds above-mentioned scope on some catalyzer.The metal active state is the catalyzer of sulfide, the metallic compound of new preparation catalyzer generally uses with oxide form, carrying out prevulcanized then handles, this treating processes can be carried out outside the field of employment, carry out but be preferably within the field of employment, particularly under the condition similar, carry out to practical application.Metal component can be attached on the inorganic amorphous carrier, as silicon-dioxide, aluminum oxide or silicon-dioxide one aluminum oxide.Can use various technology, comprise dipping, soak and be total to mulling, metal component is attached on the refractory oxide.Used catalyzer can be amorphous, the zeolite molecular sieve type or mix the zeolite molecular sieve type less in hydrocracking.Verified, the y-type zeolite of y-type zeolite and modern modification is the good catalyzer of character in petroleum base wax oil hydrogenation cracking process.In addition, can comprise dipping and ion-exchange, metal component is attached on the zeolite by any technology known in the art.For some hydrocracking process, except that zeolite, in catalyzer, also may use amorphous silicas one aluminum oxide, and the tackiness agent that in this class catalyzer, usually adopts.
According to the present invention, the common second hydrocarbon raw material F2 at the unit weight hydrogen consumption of the second reactive moieties R2 and the first hydrocarbon raw material F1 at the ratio of the unit weight hydrogen consumption of the first reactive moieties R1 greater than 2.0, can obtain good especially effect.
According to the present invention, the service temperature of the first reactive moieties R1 250 ℃～480 ℃ especially between 300～440 ℃, the first reaction effluent E1 is cooled and is cooled to below 100 ℃, is generally 25～90 ℃, is preferably 30～60 ℃ and enters then among the first cold anticyclone separate part S1 and separate.According to the present invention, pressure from the first cold anticyclone hydrogen-rich gas V1 of the first cold anticyclone separate part S1 should be approaching with the top hole pressure of the first reactive moieties R1 as far as possible, pressure difference value between the two should determine on demand, generally should not be higher than 0.8MPa, should not be higher than 0.6MPa especially.
According to the present invention, the first cold anticyclone hydrogen-rich gas V1 that contains the conventional liquid hydrocarbon of most of hydrogen among the first reaction effluent E1, foreign gas, normally gaseous hydrocarbon and small part, common compressed machine boosts and has entered among the second reactive moieties R2 that transforms the second hydrocarbon raw material F2, and the conversion product of the first cold anticyclone hydrogen-rich gas V1 and unconverted thing have finally entered the second cold anticyclone separate part S2 as the conversion product of other charging of the part of the second reaction effluent E2 and the second reactive moieties R2.Therefore the present invention has realized the repeated use of hydrogen, and partial impurities gas and the normally gaseous hydrocarbon of part that the first reactive moieties R1 is produced, and the foreign gas and the normally gaseous hydrocarbon that produce with the second reactive moieties R2 concentrate among the second reaction effluent E2.
According to the present invention, the second reactive moieties R2 preferably carries out the high consumption hydrogen hydroconversion reactions of the second hydrocarbon raw material F2.According to the present invention, the service temperature of the second reactive moieties R2 250～480 ℃, especially between 300～440 ℃.According to the present invention, the second reaction effluent E2 is separated into the second cold anticyclone hydrogen-rich gas V2 and the second cold anticyclone hydrocarbon liquid L2 at the second cold anticyclone separate part S2.The service temperature of the second cold anticyclone separate part S2 below 100 ℃, especially be generally 25～90 ℃, be preferably 30～60 ℃, the working pressure of the second cold anticyclone separate part S2, should be approaching as far as possible with the top hole pressure of the second reactive moieties R2, pressure difference value between the two should determine on demand, generally be not higher than 1.5MPa, especially be not higher than 1.0MPa, preferably be not higher than 0.7MPa.
According to accompanying drawing 2 of the present invention, at least a portion second cold anticyclone hydrogen-rich gas V2 can be returned the first reactive moieties R1 or/and the second reactive moieties R2 recycles.As required, particularly carry out under the situation of high-sulfur raw material hydrodesulfurization reaction at the first reactive moieties R1, the second cold anticyclone hydrogen-rich gas V2 may need earlier through taking off the H2S treating part, generate one and take off the cold anticyclone hydrogen-rich gas of H2S and return reactive moieties, the depriving hydrogen sulphide method of recommendation is an amine liquid absorption process.According to the present invention, the hydrogen volume concentration from the hydrogen gas stream of cold anticyclone separate part S2 of returning reactive moieties should not be lower than 70%, do not declare especially and be lower than 75%, preferably be not less than 80%.
According to accompanying drawing 2 of the present invention, the hydrogen volume concentration that enters the cold low hydrogen-rich gas V4 of first reactive moieties should not be lower than 75%, should not be lower than 80% especially, these hydrogen-rich gases are from the separating step of the second cold anticyclone hydrocarbon liquid L2: the second cold anticyclone hydrocarbon liquid L2 is depressurized under 2.5～15.0MPa pressure condition, be generally below 100 ℃ in temperature, reduce to 25～85 ℃ especially, preferably under 30～65 ℃ the condition, enter cold low separate part S4, be separated into cold low hydrogen-rich gas V4 and cold low hydrocarbon liquid L4 at this.
According to accompanying drawing 2 of the present invention, the operational condition of the second cold anticyclone separate part S2, cold low separate part S4, under the condition of recommending, the volumetric concentration that should guarantee hydrogen among the cold low hydrogen-rich gas V4 is not less than 75% or higher, wherein, the temperature of the temperature of cold low separate part S4 and the second cold anticyclone separate part S2 is basic identical.The present invention can reduce the device hydrogen loss by reclaiming the dissolved hydrogen among the hydrocarbon liquid L2.
According to the present invention, cold low hydrocarbon liquid L4 is depressurized to 0.5～5.0MPa and forms gas, the logistics of liquid mixed phase under the constant substantially condition of holding temperature, enters cold low separate part S5 then and is separated into cold low gas V5 and cold low hydrocarbon liquid L5.The working pressure of cold low separate part S5 is compared basic identical or slightly high 0.3～1.4MPa with the working pressure of cold low separate part S3.
When not using cold low separate part S5 step, cold low hydrocarbon liquid L4 may directly import such as in the such further course of processing of fractionation, but recommends to use low pressure separate part S5.
New hydrogen volume concentration should greater than 90% (volume), especially greater than 95% (volume), more preferably greater than 98% (volume).When first reactive moieties was used noble metal catalyst, the hydrogen sulfide volume content should be lower than 1PPm in the new hydrogen.
When not using cold low separate part S3 step, the first cold anticyclone hydrocarbon liquid L1 may import such as in the such further course of processing of fractionation, but exemplary application low pressure separate part S3.
Temperature and pressure condition such as following table as each step 1 of the present invention:
Figure BSA00000440256400181
Each step of the present invention is temperature and pressure condition such as following table preferably:
Figure BSA00000440256400182
Typical assembled scheme sees Table 1, only is the usefulness of giving an example, and application of the present invention is not constituted to limit.
The typical assembled scheme of table 1
Figure BSA00000440256400192
The present invention first reactive moieties R1 carries out petroleum base distillate medium-pressure hydrocracking refining reaction, can obtain good especially effect under the situation of second reactive moieties R2 execution high pressure coal tar hydrogenation modification reaction.
The described first reactive moieties R1 or the second reactive moieties R2, the reaction process that any additional sulphur can be added this reactive moieties as required, to guarantee necessary minimum concentration of hydrogen sulfide, guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer of reaction process is not less than minimum must value: such as 800PPm or 1000PPm.Described additional sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide the coal-tar 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.
In the present invention's first hydrocracking part, the raw material oil-hydrogen mixture contacts the effect of generation expection with catalyzer under the hydrocracking condition, and produce the logistics that one is referred to as reaction effluent usually, usually this logistics is at first carried out heat exchange with one or more strands of materials, then, reaction effluent further cools to about 50 ℃ lesser temps by interchanger, air-cooler or watercooler.At last, through cooled mixed phase logistics, its gas phase is by a large amount of H 2And H 2S, H 2O, lighter hydrocarbons such as CH 4, C 2H 6Deng composition, its liquid phase is made up of the hydrocarbon or the hydrocarbon component of condensation, in the reaction effluent liquid phase water is arranged usually.Then, described mixed phase logistics enters a gas, liquid/gas separator.At this, as circulating hydrogen, the liquid phase of telling goes separate part to reclaim product to the gas of telling after possible processing.Owing to contain H in the reaction effluent 2S, NH 3Even HCl is arranged, and therefore when cooling off, it can form solid precipitation (amassing), and these sedimentary major ingredient are NH 4Cl and/or many sulphur ammonia.These precipitations can reduce the heat exchanger rate of heat transfer and cause the pressure drop that exceeds the quata.When first hydrocarbon raw material contains sulphur, nitrogen, empirical method that the common process of recycle hydrogen flow process adopts be set be in the interchanger upstream that the injecting steam water of condensation becomes to prevent precipitation form so that described solid precipitation is flushed out interchanger in reaction effluent.Water in the reaction effluent may also comprise water that raw material oxycompound hydrocracking generates or/and as the water that carries of stock oil.The cooling reaction effluent can generate one usually and contain by H in the reaction effluent 2S, NH 3Separable (free) water of the mixture of the soluble salt compounds that generates.According to the present invention, when using wash-down water,, be separated into cold high score oil, cold high score gas and cold high score water at the cold anticyclone separate part, water component derives from the generation water and or the outside washing water of hydrogenation process in the cold high score water.At the cold anticyclone separate part,, can not add outside wash-down water, but this situation is rare if enough height of raw material hydrocarbon oxygen level or nitrogen content are enough low when making hydrogenation reaction effluent contain abundant water therefore not need outside wash-down water.
Characteristics of first hydrocracking part of the present invention are, owing to do not have recycle hydrogen or only exist and lacked recycle hydrogen, impurity composition, conventional gas hydrocarbon component is eliminated or has been eliminated by major part in the build-up effect of first reactive moieties, in most cases, the notes wash-down water process of the first reaction effluent E1 can be cancelled, first cold high pressure separator carries out vapour, liquid two is separated and gets final product, impurity composition among most of first reaction effluent E1, the impurity composition that the conventional gas hydrocarbon component and second reactive moieties produce, conventional gas hydrocarbon component merges at the second cold anticyclone separate part to be handled, therefore can simplify flow process, reduce investment.
At the second cold anticyclone separate part S2, the second reaction effluent E2 usually earlier reduces temperature (generally being and the second reactive moieties raw material heat exchange) to about 220～100 ℃ (this temperature should be higher than sulphur hydrogenation ammonia Tc), mixes second 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 second reaction effluent, and the aqueous solution behind the absorption ammonia must absorb the hydrogen sulfide in second reaction effluent.The described second cold anticyclone separate part comprises cooling, the separating step of second reaction effluent after the water filling, second 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, after the water filling in second reaction effluent water vapor be condensed into liquid phase gradually, hydrogen sulfide after ammonia after the absorption water filling in second reaction effluent and the further absorption water filling in second reaction effluent forms the second cold high score water liquid.Second reaction effluent cooling and in second cold high pressure separator, being separated into after the final described water filling: second a cold anticyclone hydrogen-rich gas V2 gas of on volume, mainly forming, the second cold anticyclone hydrocarbon liquid L2 and main ammoniated second a cold high score water W2 liquid of forming by water of mainly forming by the conventional liq hydrocarbon by hydrogen.The described second cold high score water W2, wherein the content of ammonia is generally 1～15% (w), is preferably 3～8% (w).Definite principle of washing water injection rate is, on the one hand, washing water are divided into vapour phase water and liquid phase water after injecting second reaction effluent, and 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 injecting washing water is the ammonia that absorbs second reaction effluent at the second cold anticyclone separate part, the ammonia concentration that prevents the second cold anticyclone hydrogen-rich gas V2 is too high, gather at reactive system, reduce catalyst activity, the ammonia concentration of the common second cold anticyclone hydrogen-rich gas V2 is low more good more, generally is not more than 200PPm, preferably is not more than 50PPm; On the one hand, the direct purpose of another of washing water is the hydrogen sulfide that absorbs simultaneously in second reaction effluent again, prevents that the process that cools of second reaction effluent from forming sulphur hydrogenation ammonia or many sulphur ammonia crystallization obstruction heat exchanger channel, increases system pressure drop.The described second cold anticyclone separate part, its second cold high pressure separator working pressure is that the second reactive moieties pressure deducts true pressure and falls, the difference of the second cold high pressure separator pressure and the second reactive moieties pressure, should not cross low or too high, be generally 0.5～1.2MPa, be preferably 0.5～0.8MPa.The described second cold anticyclone hydrogen-rich gas V2 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).According to the present invention, as previously mentioned at least a portion, be generally 85～100% the described second cold anticyclone hydrogen-rich gas V2 and enter the second reactive moieties journey and use.In order to improve plant investment efficient, must guarantee that the second cold anticyclone hydrogen-rich gas V2 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 the described second cold anticyclone hydrogen-rich gas V2 of a part (hereinafter to be referred as second cold anticyclone hydrogen-rich gas discharging gas) to get rid of methane, the ethane that reaction produces.For second cold anticyclone hydrogen-rich gas 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.
Sometimes the reaction effluent separation process scheme is not directly to cool off and the single-stage separation method, but more complicated separation method such as US3402122, US3586619, US3371029, US3371030, US4159937, US384799 or the described method of Chinese patent CN8919875.First hydrocracking of the flow process of the present invention part or the second hydrocracking part, its reaction effluent separation method can use any suitable separation method, for example can be cold minute flow process or thermoanalysis journey.
A kind of hydrocarbon hydroconversion process mode is the secondary hydrocracking, liquid phase stream that the high-pressure separator of first step hydroconversion zone is told (or its fractionation by distillation logistics) and the second stage hydroconversion zone that enters the downstream after the hydrogen of some amount mixes, described second stage hydroconversion zone can be operated under similar or significantly different conditions, and can use the catalyzer that is different from the use of first step hydroconversion zone.For example, heavy oil fraction or coal tar at first carry out hydrofining at first step hydroconversion zone, and the liquid-phase product of first step hydroconversion zone enters second stage hydroconversion zone reactor to carry out the hydrogenation hydrocracking then.Up to now, a kind of or two kinds of hydrocracking technical process partly of existing multiple different use.The variation of technical process has: the reactor in product to the first district in a circulation part first district, or the specific product in a circulation part second district (generally be heavy component) is to the reactor in first district, or the specific product in a part of second district of circulating (generally be heavy component) is to the reactor in second district.Flow process of the present invention can be applicable to various possible modified flow, and the present invention can be used for the first step or the second stage of secondary hydroconversion process.
The method that accompanying drawing 2 is described comprises that also low pressure is converted to the energy input of highly compressed logistics and is converted to the energy recovery of the logistics of low pressure from high pressure, to improve energy utilization efficiency.The conventional equipment of use as turbine so perhaps uses the conventional equipment intake in process as pump or compressor to reclaim these energy from process.
When the second reactive moieties R2 of second hydrocracking part uses a plurality of reactors, V1 can enter in the middle of the arbitrary reactor inlet or reactor of second reactive moieties, or enter the second reactive moieties R2 and contact with its beds with any other effective means, V1 contacts the mode of the second reactive moieties R2 beds, is not subjected to any restriction.Such as the pressure lower-most point that can enter the second reactive moieties hydrogen recycle loop (circulating hydrogen compressor inlet) or pressure vertex (circulating hydrogen compressor outlet) or any reactor.
Major advantage of the present invention is:
1. first reactive moieties utilizes the new hydrogen of second reactive moieties to satisfy first reaction process recycle hydrogen quantity (hydrogen to oil volume ratio in other words) requirement, reduced the special-purpose recycle hydrogen amount that first reactive moieties exists significantly, therefore, one of effect of the present invention is ideally to cancel the first circulating hydrogen compressor system, thereby significantly reduces investment outlay; Therefore, the present invention is suitable for the combination that reaction process hydrogen consumption differs bigger hydrocarbon hydroconversion process, is suitable for the combination of petroleum base fraction oil hydrogenation refining process and coal tar hydrogenating conversion process especially;
Therefore 2. the new hydrogen of first reactive moieties and second reactive moieties has been realized uniting compression and has been boosted, and two of effect of the present invention are, realized compressor maximization, reduced make-up hydrogen compressor platform number, cut down the consumption of energy simultaneously thereby significantly saved investment;
3. because most of foreign gas hydrogen sulfide, ammonia that first reactive moieties produces can directly enter second reactive moieties, when condition is suitable, the first reaction effluent sepn process can not water filling, can slow down the first cold anticyclone separate part burn into simplified system significantly;
4. most of foreign gas hydrogen sulfide of processing first reactive moieties generation of sulfur-bearing oil has entered second reactive moieties, thereby improved concentration of hydrogen sulfide in the second reaction process gas, second reactive moieties for reconstructed coal tar, can reduce the consumption that replenishes sulphur significantly, realize the sulphur resource complementation of rich sulphur oil of first raw material hydrocarbon and the rich nitrogen oil of second raw material hydrocarbon; When the first reactive moieties activity of hydrocatalyst state is sulfide type, usually need to inject sulfur supplementary agent to guarantee the concentration of hydrogen sulfide of necessary reaction gas flow, because the first reactive moieties recycle hydrogen flow rate is far below the second reactive moieties recycle hydrogen flow rate, the first reactive moieties sulfur supplementary agent consumption is much lower; The present invention is particularly suitable for low hydrogen consumption unifining process, the wax oil hydrogenation sweetening process refining such as gasoline and diesel hydrogenation that the first reactive moieties R1 carries out high-sulfur oils, the second reactive moieties R2 carries out high hydrogen consumption hydrogenation process such as the extensive hydrocracking process of wax oil, coal tar hydrogenation modification process, significantly special result;
5. first reactive moieties is suitable for not having hydrogen sulfide hydrogenation process, such as noble metal catalyst deeply de-aromatizing hydrogenation unit.
6. the first reactive moieties hydrogen purity height can effectively reduce the operation stagnation pressure, reduces construction investment;
7. because the second cold anticyclone separate part pressure is higher than the first cold anticyclone separate part pressure, simple process flow can realize that the second cold high score oil is partly dissolved the recovery of hydrogen: the 3rd separate part is set, the 3rd gas enters the first cold anticyclone separate part and utilizes the first cold high score oil dissolving power to remove the part hydro carbons, then hydrogen component use compressor C2 finish the compression enter second reactive moieties, do not need to be provided with dedicated compressor; When the 3rd gas density of hydrogen was lower than the first cold high score gas density of hydrogen, effect was obvious;
8. because the second cold anticyclone separate part pressure is higher than the first cold anticyclone separate part pressure, simple process flow can realize that the hydrogen of the second cold high score discharging gas reclaims: the second cold high score discharging air film separation and recovery system can be set, the membrane sepn hydrogen product directly enters compressor C2 inlet, use compressor layer C2 and finish and put forward dense hydrogen loop compression, do not need to be provided with dedicated compressor; When the second cold high score gas density of hydrogen is low when needing the useless hydrogen of discharging second, can reclaim the hydrogen in the second useless hydrogen easily;
9. because the second cold anticyclone separate part pressure is higher than the first cold anticyclone separate part pressure, the second cold high score water can rely on self pressure to enter the first cold anticyclone separate part, second reactive moieties for reconstructed coal tar, the first cold anticyclone separate part that the second cold high score water that free ammonia content is high enters high first reactive moieties of processing sulphur content absorbs the hydrogen sulfide in first reaction effluent, be equivalent to set up the first cold high score gas ammonia water depriving hydrogen sulphide system, can reduce the hydrogen sulfide content in the first cold high score gas significantly; For the first hydroconversion process generation high-sulfur oils hydrogenation deep desulfuration reaction process, second hydroconversion process combination of high nitrogen oil hydrogenation advanced nitrogen reaction process takes place, effect is obvious;
10. the present invention is suitable for the first cold high score gas and finally enters there is not harmful effect in the second cold anticyclone separate part to the second cold high score oil quality situation.By making the first cold high score gas experience its beds, can weaken hydro carbons that the first cold high score gas carries to the second cold high score oil quality effect by second reactive moieties.
Embodiment one
When going into operation, calculated in device year by 8000 hours/year.
First hydrogenation process, its hydrocarbon raw material F1 boiling range are 180～360 ℃ petroleum base delayed coking diesel oil, F1 sulphur content 0.870% weight, nitrogen content 0.12% weight, and (20 ℃ of volumetric flow rates are 52.3m to F1 flow rate 45t/h 3/ h), the F1 hydrofining reaction carries out reactions such as desulfurization, denitrogenation, aromatic hydrocarbons be saturated in a reactor that uses 2 Hydrobon catalyst beds, and the sulphur content of the hydrofining diesel oil of production is lower than 100PPm.First hydrogenation conditions is: temperature is that 320～370 ℃, pressure are the middle press strip spare of 6.4～8.0MPa, and this unifining process raw material hydrocarbon unit hydrogen consumption (comprising dissolved hydrogen) is 1.05% (5253Nm 3/ h), the reactor inlet hydrogen to oil volume ratio is 500, reactor inlet hydrogen volume absolute quantity is 26150Nm 3/ h, the second beds cold hydrogen quantity that enters the mouth is less than 7000Nm 3/ h, the two addition, promptly first hydrogenation process is less than 33150Nm with amount of hydrogen 3/ h.
Second hydrogenation process, its hydrocarbon raw material F2 is that boiling range is 165～505 ℃ of coal-tar middle oil distillates, F2 sulphur content 0.65% weight, nitrogen content 0.87% weight, F2 flow rate 62.5t/h, this hydrogenation process raw material hydrocarbon unit hydrogen consumption (comprising dissolved hydrogen) is 6.25% (43430Nm 3/ h).The F2 hydrocracking process adopts the secondary work flow, and the first step is that hydro-upgrading process, the second stage are " heavy gas oil+wax oil " (conventional boiling point between 335～505 ℃ hydro-upgrading wax oil) hydrocracking process.First step hydro-upgrading process hydrogenation conditions is: temperature is that 320～400 ℃, pressure are the condition of high voltage of 16.0～18.0MPa, first reactor inlet amounts of hydrogen 125000Nm 3/ h (hydrogen to oil volume ratio is 2000), beds such as first step hydro-upgrading process uses that hydrodemetallation (HDM), deoxidation, alkene are saturated, desulfurization, denitrogenation, aromatic hydrocarbons are saturated, this hydro-upgrading process raw material hydrocarbon unit hydrogen consumption (comprising dissolved hydrogen) is 5.05% (35091Nm3/h,), the target of second stage reaction process is to make hydrocracking raw material oil 50% (weight) of having an appointment be converted into boiling point and be lower than 335 ℃ conversion product, realizes full the conversion for convert hydrocarbons all is recycled to the second reactive moieties cracking catalyst bed.
By the present invention, above-mentioned two processes are combined, first reaction process and the new hydrogen logistics of second reaction process H are pressurized to 8.5MPa and all enter first reactive moieties, the first reaction effluent E1 adopts cold high score flow process, and the first cold anticyclone hydrogen-rich gas is pressurized to 18.5MPa and all enters second reaction process
The main operational condition of its each step sees the following form:
Figure BSA00000440256400261
Figure BSA00000440256400271
Embodiment according to above-mentioned condition operation, the cold low hydrogen-rich gas V4 that discharges from cold low separate part S4 return the first cold anticyclone separate part S1 contact with the first reaction effluent E1 carry dense, components such as the part methane among the V4 are absorbed, and components such as the unabsorbed hydrogen among the V4 enter the second reactive moieties R2 with the first cold anticyclone hydrogen-rich gas V1 and recycle.
Clearly, build two covers device independent of each other with the branch of routine and compare, embodiment has realized effect of the present invention, mainly shows:
1. saved the special-purpose recycle hydrogen loop compression system of first transform portion, equipment and materials such as relevant high-tension apparatus (two circulating hydrogen compressor, circulating hydrogen compressor separating tank), unit, pipeline, instrument and correlation engineering are saved, and reduce investment outlay about 450～5,000,000 yuan;
2. the new hydrogen compressed procedure division of two reaction process merges, and is very natural, and equipment and material such as relevant high pressure unit, pipeline, instrument and correlation engineering are saved;
3. first reactor inlet hydrogen of first reactive moieties total amount 26150Nm 3/ h, hydrogen sulfide volumetric concentration index is 0.10%, hydrogen sulfide amount 26.15Nm 3/ h; First hydro-upgrading reactor inlet hydrogen total amount 125000Nm of second reactive moieties 3/ h, minimum by hydrogen sulfide volumetric concentration index is 0.10% calculating, must there be hydrogen sulfide 125Nm in conventional scheme 3/ h, the two differs 98.9Nm 3/ h amounts to hydrogen sulfide difference 4.41kgmol/h, amounts to dithiocarbonic anhydride difference 167.6kg/h, saves 1340 tons/year of dithiocarbonic anhydride consumptions, and by 0.45 ten thousand yuan of/ton calculating, annual cost is saved 6,030,000 yuan/year, and this is a big benefit;
4. cancel the notes wash-down water process of the first reaction effluent E1, saved more than 70 ten thousand yuan of construction investments.
If consider other income, superiority of the present invention is just more outstanding.
Embodiment two
Based on embodiment one, the first hydrocarbon raw material F of the present invention's first reactive moieties processing is the narrow fraction diesel oil of second reaction effluent fractionation part, the narrow fraction diesel boiling range be 170～350 ℃, sulphur content 3PPm (weight), nitrogen content 8PPm (weight), aromaticity content 43% (weight), cetane value 27, (20 ℃ of volumetric flow rates are 39.8m to F1 flow rate 35t/h 3/ h), the F1 hydrofining reaction carries out reactions such as aromatic hydrocarbons is saturated in the reactor of 2 noble metal hydrogenation deeply de-aromatizing beds of a use, and the first reactive moieties reactant gases hydrogen sulfide volumetric concentration is lower than 2PPm; The sulphur content of the hydrofining diesel oil of producing is lower than 1PPm, nitrogen content is lower than 1PPm, and aromaticity content is lower than 5%, cetane value about 37.First hydrogenation conditions is: temperature is that 220～300 ℃, pressure are the condition of high voltage of 14.0～18.0MPa, and this unifining process raw material hydrocarbon unit hydrogen consumption (comprising dissolved hydrogen) is 0.85% (3308Nm 3/ h), the reactor inlet hydrogen to oil volume ratio is 800, reactor inlet hydrogen volume absolute quantity is 31840Nm 3/ h, the second beds cold hydrogen quantity that enters the mouth is less than 2500Nm 3/ h, the two addition, promptly first hydrogenation process is less than 34340Nm with amount of hydrogen 3/ h.
By the present invention, two processes are combined, after being pressurized to 18.5MPa, first reaction process and the new hydrogen logistics of second reaction process FH be divided into two-way, and one tunnel flow rate is 34340Nm 3/ h enters first reactive moieties, remains new hydrogen by-passing and enters the second reaction process reactor, and the first cold anticyclone hydrogen-rich gas enters the second cold anticyclone separate part.
Second hydrogenation process, its hydrocarbon raw material F2 is that boiling range is 165～505 ℃ of coal-tar middle oil distillates, the F2 hydrocracking process adopts the secondary work flow, and the first step is that hydro-upgrading process, the second stage are wax oil (conventional boiling point between 350～505 ℃ hydro-upgrading wax oil) hydrocracking process.The boiling point that first step hydro-upgrading process generates enters first reactive moieties between 170～350 ℃ diesel oil conversion product as the first hydrocarbon raw material F1, has formed coal tar two-stage hydrogenation combination technique.
Embodiment three
Based on embodiment one, the first hydrocarbon raw material F of the present invention's first reactive moieties processing is the narrow fraction diesel oil of second reaction effluent fractionation part, the narrow fraction diesel boiling range be 170～335 ℃, sulphur content 3PPm (weight), nitrogen content 8PPm (weight), aromaticity content 42% (weight), cetane value 31, (20 ℃ of volumetric flow rates are 33.1m to F1 flow rate 29t/h 3/ h), the F1 hydrofining reaction carries out reactions such as aromatic hydrocarbons is saturated in the reactor of 2 noble metal hydrogenation deeply de-aromatizing beds of a use, and the first reactive moieties reactant gases hydrogen sulfide volumetric concentration is lower than 2PPm; The sulphur content of the hydrofining diesel oil of producing is lower than 1PPm, nitrogen content is lower than 1PPm, and aromaticity content is lower than 5%, cetane value about 38.First hydrogenation conditions is: temperature is that 260～340 ℃, pressure are the middle press strip spare of 6.4～8.0MPa, and this unifining process raw material hydrocarbon unit hydrogen consumption (comprising dissolved hydrogen) is 0.85% (3308Nm 3/ h), the reactor inlet hydrogen to oil volume ratio is 800, reactor inlet hydrogen volume absolute quantity is 26480Nm 3/ h, the second beds cold hydrogen quantity that enters the mouth is less than 2300Nm 3/ h, the two addition, promptly first hydrogenation process is less than 28780Nm with amount of hydrogen 3/ h.
By the present invention, two processes are combined, after being pressurized to 8.5MPa, first reaction process and the new hydrogen logistics of second reaction process FH be divided into two-way, and one tunnel flow rate is 28780Nm 3/ h enters first reactive moieties, remains that new hydrogen by-passing mixes with the first cold anticyclone hydrogen-rich gas after compressor boost enters second reaction process to 18.5MPa.
Second hydrogenation process, its hydrocarbon raw material F2 is that boiling range is 165～505 ℃ of coal-tar middle oil distillates, the F2 hydrocracking process adopts the secondary work flow, and the first step is that hydro-upgrading process, the second stage are " heavy gas oil+wax oil " (conventional boiling point between 335～505 ℃ hydro-upgrading wax oil) hydrocracking process.The boiling point that first step hydro-upgrading process generates enters first reactive moieties between 170～335 ℃ diesel oil conversion product as the first hydrocarbon raw material F1, has formed coal tar two-stage hydrogenation combination technique.
Three invention effects that embodiment shows are present in the combination of other any suitable hydrocarbon hydroconversion process equally.

Claims (22)

1. a converting and combining method for hydrogenation of hydrocarbon is characterized in that, comprises following steps:
1. at the first reactive moieties R1, the new hydrogen FH and the first hydrocarbon raw material F1 generate first a reaction effluent E1 who contains components such as hydrogen, hydro carbons through hydroconversion reactions;
2. the first reaction effluent E1 finishes a cold anticyclone sepn process at the first cold anticyclone separate part S1, generates the first cold anticyclone hydrogen-rich gas V1 and first a cold anticyclone hydrocarbon liquid L1 who contains most of conventional liq hydrocarbon component among the first reaction effluent E1 who contains most of hydrogen among the first reaction effluent E1, most of conventional gas hydrocarbon component and small part conventional liq hydrocarbon component;
3. the described first cold anticyclone hydrogen-rich gas V1 of at least a portion is imported the 4. described second reactive moieties R2 of step;
4. at the second reactive moieties R2, the second hydrocarbon raw material F2 generates second a reaction effluent E2 who contains components such as hydrogen, hydro carbons through hydroconversion reactions under the hydrogen existence condition;
5. the second reaction effluent E2 finishes a cold anticyclone sepn process at the second cold anticyclone separate part S2, generate one contain most of hydrogen among the second reaction effluent E2, most of conventional gas hydrocarbon component and small part conventional liq hydrocarbon component the second cold anticyclone hydrogen-rich gas V2 and second a cold anticyclone hydrocarbon liquid L2 who contains most of conventional liq hydrocarbon component among the second reaction effluent E2.
2. combined method according to claim 1, its feature further is: at least a portion second cold anticyclone hydrogen-rich gas V2 returns the second reactive moieties R2 and recycles.
3. combined method according to claim 1, its feature further is: a part of second cold anticyclone hydrogen-rich gas V2 puies forward dense part through membrane sepn hydrogen and obtains one and carry dense hydrogen and return the second reactive moieties R2 and recycle.
4. combined method according to claim 2, its feature further is: the hydrogen volume concentration of the second cold anticyclone hydrogen-rich gas V2 is higher than 70%.
5. combined method according to claim 2, its feature further is: the hydrogen volume concentration of the second cold anticyclone hydrogen-rich gas V2 is higher than 75%.
6. combined method according to claim 1, its feature further is: the second hydrocarbon raw material F2 at the unit weight hydrogen consumption of the second reactive moieties R2 and the first hydrocarbon raw material F1 at the ratio of the unit weight hydrogen consumption of the first reactive moieties R1 greater than 2.0.
7. according to the combined method of claim 1, its feature further is: the working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 3.0MPa at least.
8. according to the combined method of claim 1, its feature further is: the working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 5.0MPa at least.
9. according to the combined method of claim 1, its feature further is: the first hydrocarbon raw material F1 is 100～550 ℃ of petroleum base hydrocarbon compositions by conventional boiling spread mainly, and the second hydrocarbon raw material F2 is 100～530 ℃ of coal-tar base hydrocarbon compositions by conventional boiling spread mainly.
10. according to the combined method of claim 1, its feature further is: the catalyzer of the first reactive moieties R1 is the deeply de-aromatizing noble metal catalyst of anti-sulphur not.
11. according to the combined method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10, its feature further is:
1. the service temperature of the first reactive moieties R1 is 250～480 ℃, and working pressure is 3.5～20.0MPa;
2. the service temperature of the first cold anticyclone separate part S1 is below 100 ℃; The special-purpose circulating hydrogen compressor of first reactive moieties is not set;
4. the service temperature of the second reactive moieties R2 is 250～480 ℃, and working pressure is 3.5～28.0MPa;
5. the service temperature of the second cold anticyclone separate part S2 is below 100 ℃.
12. according to the combined method of claim 11, its feature further is:
1. the service temperature of the first reactive moieties R1 is 300～440 ℃, and working pressure is 3.5～15.0MPa;
2. the first cold anticyclone separate part S1 service temperature is 30～65 ℃; The special-purpose circulating hydrogen compressor of first reactive moieties is not set;
4. the service temperature of the second reactive moieties R2 is 300～440 ℃, and working pressure is 8.0～25.0MPa;
5. the service temperature of the second cold anticyclone separate part S2 is 30～65 ℃.
13. according to the combined method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10, its feature further is to comprise the step that reclaims dissolved hydrogen among the second cold anticyclone hydrocarbon liquid L2:
At the 4th separate part S4, by reducing by the second cold anticyclone hydrocarbon liquid L2 pressure, flash distillation forms the 4th gas V4 and the 4th hydrocarbon liquid L4 who mainly is made up of hydrocarbon component that mainly are made up of hydrogen on volumetric concentration; At least a portion the 4th gas V4 is delivered to the first cold anticyclone separate part to be contacted with the first reaction effluent E1.
14. according to the combined method of claim 11, its feature further is: the step that comprises dissolved hydrogen among the following recovery second cold anticyclone hydrocarbon liquid L2:
At the 4th separate part S4, by reducing by the second cold anticyclone hydrocarbon liquid L2 pressure, flash distillation forms the 4th gas V4 and the 4th hydrocarbon liquid L4 who mainly is made up of hydrocarbon component that mainly are made up of hydrogen on volumetric concentration; At least a portion the 4th gas V4 is delivered to the first cold anticyclone separate part contact with the first reaction effluent E1, the hydrogen volume concentration of the 4th gas V4 is not less than 70%.
15. according to the combined method of claim 12, its feature further is: the step that comprises dissolved hydrogen among the following recovery second cold anticyclone hydrocarbon liquid L2:
At the 4th separate part S4, by reducing by the second cold anticyclone hydrocarbon liquid L2 pressure, flash distillation forms the 4th gas V4 and the 4th hydrocarbon liquid L4 who mainly is made up of hydrocarbon component that mainly are made up of hydrogen on volumetric concentration; At least a portion the 4th gas V4 is delivered to the first cold anticyclone separate part contact with the first reaction effluent E1, the hydrogen volume concentration of the 4th gas V4 is not less than 80%.
16. according to the combined method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10, its feature further is:
1. the first raw material hydrocarbon F1 is the petroleum base distillate, and the operational condition of the first reactive moieties R1 is: temperature is 250 ℃～480 ℃, and pressure is 3.5～20.0MPa, and the hydrogenation catalyst volume space velocity is 0.05～15hr -1, hydrogen/stock oil volume ratio is 400: 1～2000: 1; The first hydrocarbon raw material F1 in the unit weight hydrogen consumption of the first reactive moieties R1 less than 2%;
2. the service temperature of the first cold anticyclone separate part S1 is below 100 ℃; The special-purpose circulating hydrogen compressor of first reactive moieties is not set;
4. the second raw material hydrocarbon F2 is the coal-tar base distillate, and the operational condition of the second reactive moieties R2 is: temperature is 250～480 ℃, and pressure is 8.0～25.0MPa; The hydrogenation catalyst volume space velocity is 0.05～15hr -1, hydrogen/stock oil volume ratio is 400: 1～4000: 1; The second hydrocarbon raw material F2 in the unit weight hydrogen consumption of the second reactive moieties R2 greater than 3%; The working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 3.0MPa at least;
5. the service temperature of the second cold anticyclone separate part S2 is below 100 ℃.
17. according to the combined method of claim 16, its feature further is:
1. the first hydrocarbon raw material F1 in the unit weight hydrogen consumption of the first reactive moieties R2 less than 1.5%;
2. the service temperature of the first cold anticyclone separate part S1 is 35～60 ℃;
4. the second hydrocarbon raw material F2 in the unit weight hydrogen consumption of the second reactive moieties R2 greater than 4.5%; The working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 5.0MPa at least;
5. the service temperature of the second cold anticyclone separate part S2 is 35～60 ℃.
18. according to the combined method of claim 17, its feature further is:
1. the first hydrocarbon raw material F1 in the unit weight hydrogen consumption of the first reactive moieties R2 less than 1.3%;
2. the service temperature of the first cold anticyclone separate part S1 is 40～55 ℃;
4. the second hydrocarbon raw material F2 in the unit weight hydrogen consumption of the second reactive moieties R2 greater than 5.5%; The working pressure of the second reactive moieties R2 is than the working pressure height of first reactive moieties R1 7.0MPa at least;
5. the service temperature of the second cold anticyclone separate part S2 is 40～55 ℃.
19. according to the combined method of claim 1, its feature further is:
1. the first hydrocarbon raw material F1 is the fractionation portioned product of the second reaction effluent E2, and the first hydrocarbon raw material F1 mainly is made of low-sulfur, low nitrogen diesel component, and the catalyzer of the first reactive moieties R1 is the deeply de-aromatizing noble metal catalyst of not anti-sulphur.
20. according to the combined method of claim 16, its feature further is:
1. the first hydrocarbon raw material F1 is the fractionation portioned product of the second reaction effluent E2, and the first hydrocarbon raw material F1 mainly is made of low-sulfur, low nitrogen diesel component, and the catalyzer of the first reactive moieties R1 is the deeply de-aromatizing noble metal catalyst of not anti-sulphur.
21. according to the combined method of claim 17, its feature further is:
1. the first hydrocarbon raw material F1 is the fractionation portioned product of the second reaction effluent E2, and the first hydrocarbon raw material F1 mainly is made of low-sulfur, low nitrogen diesel component, and the catalyzer of the first reactive moieties R1 is the deeply de-aromatizing noble metal catalyst of not anti-sulphur.
22. according to the combined method of claim 1, its feature further is:
1. the 3rd hydrocarbon raw material F3 is the fractionation portioned product of the first reaction effluent E1.
CN2011100467481A 2011-02-19 2011-02-19 Hydrocarbon hydrogenation conversion process combined method Pending CN102146298A (en)

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CN105419866A (en) * 2015-11-03 2016-03-23 朱广英 Method for hydro-conversion of hydrocarbon by using thermal high-pressure separation oil pressure pump
CN105861044A (en) * 2016-03-21 2016-08-17 何巨堂 Combination method for hydrogen compressors used in hydroconversion of different raw hydrocarbon materials
CN106590737A (en) * 2015-10-20 2017-04-26 中国石油化工股份有限公司 Method for processing high aromatic hydrocarbon inferior raw oil
CN108342214A (en) * 2017-01-22 2018-07-31 何巨堂 The hydrogen usage of the hydrogenation process and online second hydrogenation process of richness production foreign gas
CN110373225A (en) * 2018-04-26 2019-10-25 洛阳瑞华新能源技术发展有限公司 Usage of the rich aromatic hydrocarbons wax oil in heavy oil up flow type heat from hydrogenation cracking reaction process
CN113460970A (en) * 2021-06-29 2021-10-01 中南大学 Device and method for green separation and purification of sulfur in desulfurization waste liquid
CN113913214A (en) * 2021-11-03 2022-01-11 何巨堂 Two-stage series hydrogenation method for waste lubricating oil in hydrogen-containing gas purification step
CN114133956A (en) * 2021-12-14 2022-03-04 洛阳瑞华新能源技术发展有限公司 Combined method of waste mineral oil upflow pre-hydrogenation process and high-hydrogen-consumption oil hydrogenation process

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CN101892077A (en) * 2010-02-23 2010-11-24 何巨堂 Two-stage hydrocarbon hydrogenation method with serial high-pressure parts

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CN1260376A (en) * 1999-03-08 2000-07-19 中国石化集团洛阳石油化工工程公司 Converting and combining method for hydrogenation of hydrocarbon
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106590737A (en) * 2015-10-20 2017-04-26 中国石油化工股份有限公司 Method for processing high aromatic hydrocarbon inferior raw oil
CN106590737B (en) * 2015-10-20 2018-07-31 中国石油化工股份有限公司 A method of the high aromatic hydrocarbons inferior feedstock oil of processing
CN105419866A (en) * 2015-11-03 2016-03-23 朱广英 Method for hydro-conversion of hydrocarbon by using thermal high-pressure separation oil pressure pump
CN105861044A (en) * 2016-03-21 2016-08-17 何巨堂 Combination method for hydrogen compressors used in hydroconversion of different raw hydrocarbon materials
CN108342214A (en) * 2017-01-22 2018-07-31 何巨堂 The hydrogen usage of the hydrogenation process and online second hydrogenation process of richness production foreign gas
CN110373225A (en) * 2018-04-26 2019-10-25 洛阳瑞华新能源技术发展有限公司 Usage of the rich aromatic hydrocarbons wax oil in heavy oil up flow type heat from hydrogenation cracking reaction process
CN113460970A (en) * 2021-06-29 2021-10-01 中南大学 Device and method for green separation and purification of sulfur in desulfurization waste liquid
CN113913214A (en) * 2021-11-03 2022-01-11 何巨堂 Two-stage series hydrogenation method for waste lubricating oil in hydrogen-containing gas purification step
CN114133956A (en) * 2021-12-14 2022-03-04 洛阳瑞华新能源技术发展有限公司 Combined method of waste mineral oil upflow pre-hydrogenation process and high-hydrogen-consumption oil hydrogenation process

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