CN102433156B

CN102433156B - A kind of different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation transforms combined method

Info

Publication number: CN102433156B
Application number: CN201110311390.0A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-10-03
Filing date: 2011-10-03
Publication date: 2016-03-16
Anticipated expiration: 2031-10-03
Also published as: CN102433156A

Abstract

A kind of different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation transforms combined method, be that to complete aromatic hydrogenation in the first hydrogenation reaction part saturated for the first hydrocarbon fraction of the heavy fraction composition of 265 ~ 450 DEG C primarily of boiling point, first hydrogenation reaction effluent completes hydrocracking in the second hydrogenation reaction part, be that to complete aromatic hydrogenation in the 3rd hydrogenation reaction part saturated for the second hydrocarbon fraction of the light fraction composition of 165 ~ 265 DEG C primarily of boiling point, after the first hydrocarbon fraction hydrogenating reaction effluent and the mixing of the second hydrocarbon fraction hydrogenating reaction effluent, carry out Separation and Recovery.The stock oil that the present invention is different to boiling range selects hydroconversion reactions condition suitable separately to produce diesel oil distillate, there is optimization of catalysts configure, reduce gas yield, reduce hydrogen consumption, improve the advantages such as liquid product mass, quiet run, simple flow, be suitable for the gelatin liquefaction oil classification hydroconversion process that hydro-upgrading is oily or nitrogen content is low of liquefied coal coil.

Description

A kind of different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation transforms combined method

Technical field

The present invention relates to a kind of different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation and transform combined method, its target produces fine-quality diesel oil cut, be suitable for combination treatment and contain a large amount of twin nuclei aromatic hydrocarbons (as indenes, indenes class, naphthalene, naphthalene class and in various degree hydride) oil product and containing the aromatic hydrocarbons of a large amount of polynuclear plane (as acenaphthene, acenaphthene class, acenaphthylene, acenaphthylene class, fluorenes, fluorenes class, heterocycle fluorenes, heterocycle fluorenes class, anthracene, anthracene class, luxuriant and rich with fragrance, luxuriant and rich with fragrance class and in various degree hydride) oil product, or be suitable for processing the not only oil product containing a large amount of twin nuclei aromatic hydrocarbons but also the oil product containing a large amount of polynuclear plane aromatic hydrocarbons, its technological principle is: first according to the difference of component boiling point in raw material oil product, twin nuclei aromatic hydrocarbons and polynuclear plane aromatics seperation are obtained two fractions, then reaction conditions best is separately selected to carry out hydrocracking, particularly, the present invention relates to a kind of process direct hydrogenation liquefaction of coal oil and the converting and combining method for hydrogenation of the different boiling ranges height aromatic hydrocarbons high-density hydrocarbon ils of hydrogenation modification oily (comprising liquid fuel and hydrogenation modification oil thereof that brown coal thermally dissolving and catalytic method produces).

Background technology

The thermally dissolving and catalytic of a kind of brown coal preparing liquid fuel that patent CN100547055C states clearly is owned by France in brown coal medium-pressure hydrocracking direct liquefaction process, comprises Coal liquefaction process and liquefied coal coil hydrogenation modification process totally two processes.In order to improve the transformation efficiency of coal direct liquefaction and realize coal feedstock and enter reactor, coal makes coal dust before entering reactor usually, be made into coal oil mixture with the solvent oil possessing good hydrogen supply capacity, coal oil mixture enters reactor after pressurization, heating.

Coal liquefaction process of the present invention, refer to coal and the molecule hydrogen that may exist as raw material, with specific oil product (being generally the hydrogenation modification oil of liquefied coal coil) for hydrogen supply dissolvent oil, under certain operational condition (as service temperature, working pressure, solvent oil/coal weight ratio, hydrogen/solvent oil volume ratio and suitable hydrogenation catalyst), directly there is the reaction process of carbon-carbon bond thermally splitting, hydrogenation liquefaction in coal.

Liquefied coal coil of the present invention, refer to the oil product that described Coal liquefaction process produces, it is present in Coal Liquefaction reaction effluent, is to consume coal based on hydrogen supply dissolvent oil, reaction and react the combined reaction product of transfer hydrogen.

After Coal liquefaction process works well, hydrogen supply dissolvent oil usually adopts the hydrogenation modification oil of the self-produced liquefied coal coil of Coal liquefaction process (being generally conventional boiling range higher than the distillate of 165 DEG C), the major objective of liquefied coal coil hydrogenation modification process produces Coal liquefaction process solvent oil, be exactly specifically the content improving " there is the component of good hydrogen supply function " in oil product, such as improve cycloalkyl benzene class, the content of bicyclic alkyl benzene class component, a large amount of double ring arene and this fact of a large amount of thrcylic aromatic hydrocarbon is contained based on liquefied coal coil, liquefied coal coil hydrogenation modification process is the hydrogenation process of " appropriate aromatic saturation ".

The ultimate aim of Coal liquefaction process produces the oil product of outer confession, the hydrogenation modification oil content that usual liquefied coal coil hydrogenation modification process produces is two portions: a part is used as Coal liquefaction process hydrogen supply dissolvent oil, and a part is used as the outer oil extraction of gelatin liquefaction liquefaction process.Usually, the light oil of gelatin liquefaction at least partially that Coal liquefaction process produces is used as the outer oil extraction A of coal liquifaction process, remaining liquefied coal coil is used as liquefied coal coil hydrogenation modification process stock oil and produces Coal liquefaction process hydrogen supply dissolvent oil and outer oil extraction B, now there is the outer oil extraction of A and B two-way, the final whereabouts of the outer oil extraction of A and B two-way is all through hydroconversion process production high-quality oil product such as diesel oil distillate, naphtha fraction usually.

The liquefaction oil of the thermally dissolving and catalytic method of typical brown coal preparing liquid fuel, the light oil that liquefies, the hydrogenation modification oil of liquefaction oil, outer oil extraction hydroconversion process stock oil character are in table 1.Table 1 China and foreign countries' oil extraction is the mixing oil of oil product A and oil product B, weight ratio A: B=1: 4, be particularly suitable for producing diesel oil distillate.

Table 2 lists the part aromatic component and contrast hydride boiling point thereof and density data that occur in table 1, for comparative illustration Typical Aromatic component and the change contrasting hydride boiling point, condensation point and density thereof.

Table 1 brown coal coal liquifaction process oil property

Table 2 Typical Aromatic component and contrast hydride boiling point, condensation point and density summary sheet

Thermally dissolving and catalytic method liquefaction oil and the hydrogenation modification oil thereof of the brown coal preparing liquid fuel being representative with character listed by table 1 belong to high aromatic hydrocarbons high-density hydrocarbon ils, normally comprise the high-density oil product being rich in aromatic hydrocarbons that conventional boiling range is 165 ~ 450 DEG C of hydrocarbon components, in most cases simultaneously containing naphtha Cut with regard to its boiling range, fraction of diesel oil, two kinds in the multiple cut of heavy fraction or three kinds, usually the conventional boiling range comprising 20 ~ 65% to be the first hydrocarbon fraction (last running that namely polynuclear plane aromaticity content is high) of 265 ~ 450 DEG C and the conventional boiling range of 20 ~ 65% the be second hydrocarbon fraction (i.e. twin nuclei aromaticity content high and the lighting end that polynuclear plane aromaticity content is low) of 165 ~ 265 DEG C.Character (the such as two ring aromatic content of above-mentioned first hydrocarbon fraction and the second hydrocarbon fraction, polycyclic aromatic hydrocarbon content, nitrogen content, density, boiling point, hydrogen richness, viscosity, residual carbon content, metal content, oxygen level, sulphur content, cetane value) difference is very large, clear gusoline such as production low density is produced when double ring arene and polycyclic aromatic hydrocarbons carry out hydrocracking simultaneously, during high hexadecane value diesel oil distillate, due to the difference of component molecular structure, best reaction mechanism, reaction pressure and temperature range, catalyzer configures, hydrogen consumes, the cycle of operation, fractionation mode and quality product difference very large.Such as double ring arene hydrogen dividing potential drop needed for aromatic saturation compared with polycyclic aromatic hydrocarbons is much smaller: hydrogen dividing potential drop needed for double ring arene is generally 6.0 ~ 10.0MPa and needed for polycyclic aromatic hydrocarbons, hydrogen dividing potential drop is generally 10.0 ~ 18.0MPa, and this can reach cause the optimum operation differing pressure of hydrogenation unit at 2.0 ~ 8.0MPa.Saturated rear the produced cycloalkanes aromatic hydrocarbons of the part aromatic ring of such as double ring arene and polycyclic aromatic hydrocarbons again, the feasible desirable route being converted into diesel component is different: naphthane selective opening can realize the hydro-upgrading object of high diesel yield, and polycyclic aromatic hydrocarbons has to pass through the hydrocracking process (being difficult to selective opening) producing a large amount of low molecular weight hydrocarbon usually, this differs greatly causing best catalyst property.For processing the situation producing diesel component on a small scale, adopt conventional associating processing scheme (different boiling ranges fraction mixes the hydrofining and mild hydrocracking cascade process of carrying out processing), can simple flow, minimizing construction investment.But mass-producing processing is produced to the situation of diesel component; when a certain oil property is similar to the oil product of character listed by table 1; the size and shape difference that the second hydrocarbon fraction be the first hydrocarbon fraction and the conventional boiling range of 265 ~ 450 DEG C based on conventional boiling range being 165 ~ 265 DEG C compares mean molecule is very large, combines processing and there is following shortcoming:

1. the most suitable Hydrobon catalyst formula due to unifining process (such as hydrodenitrification, aromatic hydrogenation saturated) is inevitable different, combining processing cannot the catalyzer of selectivity the best and operational condition, as realized the hydrofining of the first hydrocarbon fraction appropriate depth, then must form excessive hydrogenation to the second hydrocarbon fraction of less carbon number to refine, increase hydrogen consumption, reduce Hydrobon catalyst efficiency;

2. hydrocracking process (such as selective hydrogenation open loop, hydrocracking) most suitable hydrocracking catalyst formula inevitable different, combining processing cannot the hydrocracking catalyst of selectivity the best and operational condition, as realized the hydrocracking of the first hydrocarbon fraction appropriate depth, then must form excessive hydrogenation cracking to the second hydrocarbon fraction of less carbon number, fall low-density hydrocracking process due to last running and there is " cracking aerogenesis " effect, the associating course of processing must cause the second hydrocarbon fraction excessively " cracking " produce non-ideal product and gaseous fraction and naphtha Cut, reduce diesel yield, increase hydrogen consumption, increase temperature rise, increase energy consumption, increase loaded catalyst,

3. combine and add man-hour, the per pass conversion upper limit that low-density hydrocracking process falls in the first hydrocarbon fraction is limited, rationally high per pass conversion can not be adopted, catalyzer and operational condition that cracking activity is rationally high can not be adopted, reason is a large amount of overcrackings that the second hydrocarbon fraction can occur, and reduces economy;

4. combine and add man-hour, the per pass conversion upper limit that low-density hydrocracking process falls in the first hydrocarbon fraction is limited, when raw material do higher cause hydrogenated oil end point temperature higher such as higher than 380 DEG C time, a small amount of last running is unsuitable for being used as diesel component and therefore must be separated with diesel component, corresponding sepn process will be increased, produce a large amount of separating energy consumption; As for avoiding the problems referred to above, stock oil utilization ratio must be reduced and go out by higher Component seperation in raw material and do not enter hydrogenation grading process;

5. under certain condition, when there is the first hydrocarbon fraction and the second hydrocarbon fraction of relative separation, combine the mixing process that processing in fact completes the first hydrocarbon fraction and the second hydrocarbon fraction, reduced the concentration value of component, sacrifice the relative separation degree formed, will separating energy consumption be increased;

6. the second hydrocarbon fraction can carry out hydrogenation reaction under lesser temps (as 320 ~ 380 DEG C) and lower pressure (as 6.0 ~ 10.0MPa), first hydrocarbon fraction just can complete hydrogenation reaction under comparatively high temps (as 360 ~ 420 DEG C) and elevated pressures (as 10.0 ~ 18.0MPa), therefore combine and add man-hour, there is following production operation danger:

A, in order to make raw material by expection transform, must according to the first hydrocarbon fraction character coupling catalyzer and reaction conditions, namely the catalyzer of comparatively high temps, elevated pressures condition and greater activity is adopted, and with this understanding, second hydrocarbon fraction speed of reaction is too fast, reaction heat gathers rapidly, causes reactor bed temperature rise to be difficult to control, even overtemperature;

B, in order to alleviate above-mentioned situation, need be forced to reduce temperature of reaction, to control bed temperature rise; After temperature reduces, lighting end be obtained by reacting alleviation, but the reaction of a part of last running can be terminated, temperature reduce after, viscosity increases, mobility is deteriorated, and hinders the flowing of lighting end and hydrogen, and heavy constituent rests on for a long time in hot environment and can not participate in hydrogenation reaction, will condensation, coking, blocking catalyst duct, so forms vicious cycle, causes beds pressure drop to be risen rapidly;

C, when there is serious overtemperature in beds, be forced to start emergency decompression, its objective is and reduce reacting system pressure rapidly, stop or significantly slow down hydrogenation reaction; For Hydrobon catalyst bed, the first hydrocarbon fraction generally at pressure lower than reaching the object significantly suppressing hydrogenation reaction speed during 9.0 ~ 10.0MPa, and the hydrogenation reaction of the second hydrocarbon fraction at pressure lower than just significantly being suppressed during 6.0MPa; When starting quick pressure releasing (such as blowdown rate is first minute 15 bas/min of clock) system, pressure is down to 9.0MPa about 3 ~ 4 minutes from 13.5MPa, namely after 3 ~ 4 minutes, the reaction of the first hydrocarbon fraction is stopped substantially, but now the reaction of the second hydrocarbon fraction is still being carried out, bed temperature continues to raise, and after pressure release starts about 7 minutes, system pressure is down to below 6.0MPa, suppresses the pressure condition of the second hydrocarbon fraction reaction just can reach; But the second hydrocarbon fraction heat that sustained reaction is released of about 7 minutes, because hydrogen flowing is not smooth during emergency decompression, reaction heat can not be carried away in time, heat accumulation is completed at beds, Hydrobon catalyst bed temperature is made to rise to more than 460 DEG C, Hydrobon catalyst has possessed quite active heat from hydrogenation cracking function, occur immediately: beds temperature runaway (temperature can rise to more than 800 DEG C) process, cause reactor body impaired, the deterioration of catalyst metal form.

For the process producing low density diesel component, when processing with the direct hydrogenation liquefaction of coal oil that is representative of character listed by table 1 and hydrogen modified oil thereof, the desirable upgrading approach of naphthalene or naphthalene series substance or indenes or indenes system thing has been first fragrant ring filling, then to this saturated rings open loop, this is a feasible program that hydrogen consumption is low, density reduction amplitude is large; The desirable upgrading approach of acenaphthene or acenaphthene system thing or fluorenes or fluorenes system thing or anthracene or anthracene system thing has been that two fragrant ring fillings (normally two aromatic rings in outside) then carry out hydrocracking open loop to this hydride, this is rational process, but must handle well under prior art conditions and significantly reduce the productive rate that density reduces petroleum naphtha and gas simultaneously as far as possible, as industrial production, the hydrocracking catalyst that should diesel yield selected as far as possible high and operational condition, reduce low carbon number byproduct output as far as possible.

For the process producing low density diesel component, when processing with the direct hydrogenation liquefaction of coal oil that is representative of character listed by table 1 and hydrogen modified oil thereof, boiling point data hint listed by table 2: with reference to indane normal boiling point (177 DEG C) and acenaphthene normal boiling point (278 DEG C), with 165 DEG C and 265 DEG C for dividing point, about normal boiling point is the cut of 165 ~ 265 DEG C will be not 2 containing the aromatic hydrocarbons of tricyclic structure and maximum ring structure numbers of most of aromatic hydrocarbons substantially, and the aromatic hydrocarbons overwhelming majority of polynuclear plane concentrates and is present in normal boiling point higher than in the cut of 265 DEG C.Therefore following operating principle can be proposed: normal boiling point is defined as polynuclear plane aromatic fraction i.e. the first hydrocarbon fraction higher than the cut of 265 DEG C, the cut of 165 ~ 265 DEG C, normal boiling point position is defined as twin nuclei aromatic fraction i.e. the second hydrocarbon fraction, optionally carry out hydrogenation aromatic saturation to the aromatic hydrocarbons of tricyclic structure to connect with hydrocracking and process, optionally carry out hydrogenation aromatic saturation to the aromatic hydrocarbons of two ring structures to process with necessary complementarity monocycle alkyl benzene selective open loop hydro-upgrading, in product diesel oil (density, cetane value) to realize hydrogen consumption under the identical condition of quality index low, diesel yield is high, energy consumption this global optimization target low, further combined separation is carried out to whole hydrogenation reaction effluents of the first hydrocarbon fraction and the second hydrocarbon fraction, to reduce construction investment.

As can be seen from perhydro fluorenes boiling point and density data listed by table 2, along with the intensification of degree of hydrogenation, the density value (20 DEG C) of the product after the aromatic hydrogenation of tricyclic structure is saturated, though significantly reduce still far above 890 kilogram/cubic metre, still need just can become fine-quality diesel oil component through hydrocracking process, but boiling point obviously reduces (fluorenes hydrogenation is perhydro fluorenes boiling point lowering about 45 DEG C), therefore raw material before hydrogenation is carried out to fractionation cutting and carries out product after hydrotreated lube base oil compared with fractionation cuts, carry out fractionation cutting to raw material before hydrogenation can obtain better " classification Cut and choose ", because the aromatic hydrogenation saturates of tricyclic structure mixes with the hydrocarbon of other number of rings lower than tricyclic structure, fractionation strategy cannot be adopted to be separated.

Based on above analysis, the present invention propose a kind of be suitable for liquefied coal coil hydrogenation modification oil or the gelatin liquefaction oil classification combined depth converting and combining method for hydrogenation of low nitrogen content, according to the technological principle of " classification hydrogenation, hydrogenation reaction effluent can combined separation ", avoid the second hydrocarbon fraction overcracking, improve diesel yield, reduce hydrogen consumption, improve process synthesis economic performance, to the greatest extent can simple flow, reduction construction investment.

About the hydrogenation modification oil of liquefied coal coil or the gelatin liquefaction oil classification combined depth converting and combining method for hydrogenation of low nitrogen content, have no report.

Obtain different boiling ranges fraction about the initial high aromatic hydrocarbons high-density hydrocarbon ils of separation, then carry out classification combined depth converting and combining method for hydrogenation, have no report.

The first object of the present invention is to provide a kind of different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation to transform combined method, and its target produces fine-quality diesel oil cut.

The second object of the present invention is the gelatin liquefaction oil classification combined depth converting and combining method for hydrogenation providing a kind of hydrogenation modification of liquefied coal coil oil or low nitrogen content, and its target produces fine-quality diesel oil cut.

The third object of the present invention be the thermally dissolving and catalytic method liquefaction oil of the hydrogenation modification oil of the thermally dissolving and catalytic method liquefaction oil that a kind of brown coal preparing liquid fuel is provided or the brown coal preparing liquid fuel of low nitrogen content classification combined depth converting and combining method for hydrogenation, its target produces fine-quality diesel oil cut.

Summary of the invention

A kind of different boiling ranges height of the present invention aromatic hydrocarbons high-density hydrocarbon oil hydrogenation transforms combined method, comprises the steps:

1. the first hydrocarbon fraction is the last running composition of 265 ~ 450 DEG C primarily of normal boiling point, first hydrocarbon fraction aromaticity content higher than 40%, density is higher than 920 kilograms/cubic metre, in the first hydrogenation reaction part, first hydrocarbon fraction carries out aromatic hydrogenation saturated reaction and is converted into the first hydrogenation reaction effluent, and the first hydrogenation conditions is: temperature is 200 ~ 460 DEG C, pressure is 5.0 ~ 30.0MPa, the first hydrogenation catalyst volume space velocity is 0.05 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1;

In the second hydrogenation reaction part, first hydrogenation reaction effluent carries out hydrocracking reaction and is converted into the second hydrogenation reaction effluent, and the second hydrogenation conditions is: temperature is 260 ~ 460 DEG C, pressure is 5.0 ~ 30.0MPa, the second hydrogenation catalyst volume space velocity is 0.05 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1; Second hydrogenation reaction effluent is used as the first hydrocarbon fraction hydrogenating reaction effluent;

2. the second hydrocarbon fraction is the lighting end composition of 165 ~ 265 DEG C primarily of normal boiling point, second hydrocarbon fraction aromaticity content higher than 40%, density is higher than 900 kilograms/cubic metre, in the 3rd hydrogenation reaction part, second hydrocarbon fraction carries out aromatic hydrogenation saturated reaction and is converted into the 3rd hydrogenation reaction effluent, and the 3rd hydrogenation conditions is: temperature is 200 ~ 460 DEG C, pressure is 5.0 ~ 30.0MPa, the 3rd hydrogenation catalyst volume space velocity is 0.05 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1; 3rd hydrogenation reaction effluent is used as the second hydrocarbon fraction hydrogenating reaction effluent;

3. the first hydrocarbon fraction hydrogenating reaction effluent and the second hydrocarbon fraction hydrogenating reaction effluent enter high pressure separate part, temperature be 30 ~ 75 DEG C, pressure be separated under being the condition of 5.0 ~ 30.0MPa high score gas and high score oil;

4. first part's high score gas enters the first hydrogenation reaction part, and second section high score gas enters the 3rd hydrogenation reaction part;

5. in high score oil separation section, be separated high score oil and obtain hydrogenation oil product.

Operational condition of the present invention is generally:

1. the first hydrocarbon fraction nitrogen content is lower than 2000PPm, and 20 DEG C of density are higher than 920 kilograms/cubic metre, and aromaticity content is higher than 40%;

In the first hydrogenation reaction part, the saturated transformation efficiency of aromatic hydrogenation of the first hydrocarbon fraction is higher than 40%, and the first hydrogenation conditions is: temperature is 300 ~ 440 DEG C, pressure is 7.0 ~ 24.0MPa, the first hydrogenation catalyst volume space velocity is 0.15 ~ 1.0hr ^-1, hydrogen/stock oil volume ratio is 600: 1 ~ 2000: 1;

In the second hydrogenation reaction part, the hydrocracking reaction that hydrocarbon ils in first hydrogenation reaction effluent completes expection makes 20 DEG C of density of 20 of the diesel component in the second hydrogenation reaction effluent DEG C of density ratio first hydrocarbon fractions reduce at least 30kg/ cubic meter, and the second hydrogenation conditions is: temperature is 300 ~ 440 DEG C, pressure is 7.0 ~ 24.0MPa, the second hydrogenation catalyst possesses gas yield is low and diesel yield is high function, the second hydrogenation catalyst volume space velocity is 0.15 ~ 1.0hr ^-1, hydrogen/stock oil volume ratio is 1000: 1 ~ 3000: 1;

In first hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 10PPm, and the cetane value of diesel component is higher than 30;

2. the second hydrocarbon fraction nitrogen content is lower than 800PPm, and 20 DEG C of density are higher than 900 kilograms/cubic metre, and aromaticity content is higher than 40%;

In the 3rd hydrogenation reaction part, the saturated transformation efficiency of aromatic hydrogenation of the second hydrocarbon fraction is higher than 40%, and the 3rd hydrogenation conditions is: temperature is 260 ~ 420 DEG C, pressure is 7.0 ~ 24.0MPa, the 3rd hydrogenation catalyst volume space velocity is 0.15 ~ 2.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 2000: 1;

In second hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 10PPm, and the cetane value of diesel component is higher than 28;

3. high pressure separate part operational condition is: temperature is 40 ~ 55 DEG C, pressure is 7.0 ~ 24.0MPa.

Operational condition of the present invention is generally:

1. the first hydrocarbon fraction nitrogen content is lower than 1000PPm, and 20 DEG C of density are higher than 940 kilograms/cubic metre, and aromaticity content is higher than 55%;

First hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

In first hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 2PPm, and the cetane value of diesel component is higher than 35;

2. the second hydrocarbon fraction nitrogen content is lower than 500PPm, and 20 DEG C of density are higher than 920 kilograms/cubic metre, and aromaticity content is higher than 55%;

3rd hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

In second hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 2PPm, and the cetane value of diesel component is higher than 30;

3. high pressure separate part operational condition is: temperature is 45 ~ 55 DEG C, pressure is 10.0 ~ 20.0MPa.

During the 4th hydrogenation reaction part that the present invention uses, operational condition is:

2. in the 4th hydrogenation reaction part, 3rd hydrogenation reaction effluent carries out double ring arene hydrogenation ring-opening reaction and is converted into the 4th hydrogenation reaction effluent, and the 4th hydrogenation conditions is: temperature is 200 ~ 460 DEG C, pressure is 5.0 ~ 30.0MPa, the 4th hydrogenation catalyst possesses highly selective double ring arene hydrogenation open loop function, the 4th hydrogenation catalyst volume space velocity is 0.05 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1; 4th hydrogenation reaction effluent is used as the second hydrocarbon fraction hydrogenating reaction effluent.

During the 4th hydrogenation reaction part that the present invention uses, operational condition is generally:

2. in the 4th hydrogenation reaction part, 3rd hydrogenation reaction effluent complete double ring arene open loop rate higher than 40% highly selective double ring arene hydrogenation ring-opening reaction be converted into the 4th hydrogenation reaction effluent, the 4th hydrogenation conditions is: temperature is 250 ~ 420 DEG C, pressure is 7.0 ~ 24.0MPa, the 4th hydrogenation catalyst possesses highly selective double ring arene hydrogenation open loop function, the 4th hydrogenation catalyst volume space velocity is 0.25 ~ 2.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 2000: 1.

First hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

3rd hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

4th hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

In order to simple flow, the present invention: 3. the first hydrocarbon fraction hydrogenating reaction effluent and the second hydrocarbon fraction hydrogenating reaction effluent enter high pressure separate part through heat exchange temperature-fall period after directly mixing.

In order to the cracking that circulates oily V to be cracked, the present invention: 5. in high score oil separation section, obtain one primarily of the to be cracked oily V of 20 DEG C of density higher than the hydrocarbon component composition of 900 kilograms/cubic metre, oily V to be cracked goes the second hydrogenation reaction part to contact with the second hydrogenation catalyst at least partially.

In order to reduce oily V circulation cracking conversion rate to be cracked, the present invention: 5. in high score oil separation section, obtain one primarily of the to be cracked oily V of 20 DEG C of density higher than the hydrocarbon component composition of 900 kilograms/cubic metre, oily V to be cracked goes the second hydrogenation reaction part to contact with the latter half hydrogenation catalyst of the second hydrogenation catalyst at least partially.

The first hydrogenation reaction part material oil nature is improved in order to utilize oily V to be cracked, the present invention: 5. in high score oil separation section, obtain one primarily of the to be cracked oily V of 20 DEG C of density higher than the hydrocarbon component composition of 900 kilograms/cubic metre, oily V to be cracked goes the first hydrogenation reaction part to contact with the first hydrogenation catalyst at least partially.

In order to reduce petroleum naphtha PAC nitrogen content, the present invention: 5. in high score oil separation section, obtain one primarily of normal boiling point be 120 ~ 170 DEG C hydrocarbon component composition petroleum naphtha PAC, part petroleum naphtha PAC goes the 3rd hydrogenation reaction part to contact with the 3rd hydrogenation catalyst.

In order to improve the character of solar oil HD1, the present invention: 5. in high score oil separation section, obtain one primarily of normal boiling point be 165 ~ 265 DEG C hydrocarbon component composition solar oil HD1, part solar oil HD1 goes the 4th hydrogenation reaction part to contact with the 4th hydrogenation catalyst.

In order to improve the character of heavy gas oil HD2, the present invention: 5. in high score oil separation section, obtain one primarily of normal boiling point be 265 ~ 330 DEG C hydrocarbon component composition heavy gas oil HD2, part heavy gas oil HD2 goes the 4th hydrogenation reaction part to contact with the latter half hydrogenation catalyst of the 4th hydrogenation catalyst.

Operational condition during the slender acanthopanax H-H reaction part that the present invention uses is:

1. the second hydrogenation reaction effluent enters slender acanthopanax H-H reaction part, complete slender acanthopanax H-H reaction and be converted into the 5th hydrofining reaction effluent, slender acanthopanax hydroformylation reaction condition is: temperature is 250 ~ 480 DEG C, pressure a little less than the second hydrogenation reaction part operation pressure, slender acanthopanax hydrogen catalyst be Hydrobon catalyst, slender acanthopanax hydrogen catalyst volume space velocity is 2.0 ~ 20.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1; 5th hydrogenation reaction effluent is used as the first hydrocarbon fraction hydrogenating reaction effluent.

Operational condition during the present invention second hydrogenation reaction effluent use thermal high separate part AHPS is:

1. the second hydrogenation reaction effluent enters thermal high separate part AHPS, be under the condition of 180 ~ 380 DEG C, be separated into hot high score gas and hot high score oil in temperature, hot high score oil is primarily of the hydrocarbon component composition of normal boiling point higher than 280 DEG C, and hot high score gas is used as the first hydrocarbon fraction hydrogenating reaction effluent.

The present invention second hydrogenation reaction effluent uses operational condition during thermal high separate part AHPS to be generally: 1. the second hydrogenation reaction effluent enters thermal high separate part AHPS, temperature be 250 ~ 350 DEG C, pressure is separated into hot high score gas and hot high score oil under being the condition of 10.0 ~ 20.0MPa, hot high score oil returns the second hydrogenation reaction part and contact with the second hydrogenation catalyst as the oily RHPO of cycling hot high score at least partially.

The weight rate of cycling hot high score oil RHPO of the present invention is generally 15 ~ 150% of the first hydrocarbon fraction weight rate.

The present invention is suitable for processing following oil product:

1. the first hydrocarbon fraction derives from following oil product: the hydrogenation modification of liquefied coal coil oil or nitrogen content are lower than the liquefied coal coil of 2000PPm or their mixing oil;

2. the second hydrocarbon fraction derives from following oil product: the hydrogenation modification of liquefied coal coil oil or nitrogen content are lower than the liquefied coal coil of 2000PPm or their mixing oil.

The present invention is particularly suitable for processing following oil product:

1. the first hydrocarbon fraction derives from following oil product: the hydrogenation modification of liquefied coal coil oil or nitrogen content are lower than the liquefied coal coil of 2000PPm or their mixing oil, and 20 DEG C of density are 920 ~ 1040 kilograms/cubic metre;

2. the second hydrocarbon fraction derives from following oil product: the hydrogenation modification of liquefied coal coil oil or nitrogen content are lower than the liquefied coal coil of 2000PPm or their mixing oil, and 20 DEG C of density are 900 ~ 960 kilograms/cubic metre.

When the present invention is applied in brown coal and presses liquefied coal coil or its hydrogenation modification oil, its operational condition is generally:

1. the first hydrocarbon fraction derives from brown coal and presses liquefied coal coil or its hydrogenation modification oil, and the first hydrocarbon fraction nitrogen content is lower than 2000PPm, and 20 DEG C of density are higher than 940 kilograms/cubic metre;

In the first hydrogenation reaction part, the saturated transformation efficiency of aromatic hydrogenation of the first hydrocarbon fraction is higher than 40%, and the first hydrogenation conditions is: temperature is 300 ~ 440 DEG C, pressure is 10.0 ~ 20.0MPa, the first hydrogenation catalyst volume space velocity is 0.15 ~ 1.0hr ^-1, hydrogen/stock oil volume ratio is 600: 1 ~ 2000: 1;

In the second hydrogenation reaction part, the hydrocracking reaction that hydrocarbon ils in first hydrogenation reaction effluent completes expection makes 20 DEG C of density of 20 of the diesel component in the second hydrogenation reaction effluent DEG C of density ratio first hydrocarbon fractions reduce at least 30kg/ cubic meter, and the second hydrogenation conditions is: temperature is 300 ~ 440 DEG C, pressure is 10.0 ~ 20.0MPa, the second hydrogenation catalyst possesses gas yield is low and diesel yield is high function, the second hydrogenation catalyst volume space velocity is 0.15 ~ 1.0hr ^-1, hydrogen/stock oil volume ratio is 1000: 1 ~ 3000: 1;

In first hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 4PPm, and the cetane value of diesel component is higher than 28;

2. the second hydrocarbon fraction derives from brown coal and presses liquefied coal coil or its hydrogenation modification oil, and the second hydrocarbon fraction nitrogen content is lower than 1000PPm, and 20 DEG C of density are higher than 915 kilograms/cubic metre;

In the 3rd hydrogenation reaction part, the saturated transformation efficiency of aromatic hydrogenation of the second hydrocarbon fraction is higher than 40%, and the 3rd hydrogenation conditions is: temperature is 260 ~ 420 DEG C, pressure is 10.0 ~ 20.0MPa, the 3rd hydrogenation catalyst volume space velocity is 0.15 ~ 2.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 2000: 1;

In the 4th hydrogenation reaction part, 3rd hydrogenation reaction effluent complete double ring arene open loop rate higher than 40% highly selective double ring arene hydrogenation ring-opening reaction be converted into the 4th hydrogenation reaction effluent, the 4th hydrogenation conditions is: temperature is 250 ~ 420 DEG C, pressure is 10.0 ~ 20.0MPa, the 4th hydrogenation catalyst possesses highly selective double ring arene hydrogenation open loop function, the 4th hydrogenation catalyst volume space velocity is 0.25 ~ 2.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 2000: 1;

In second hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 4PPm, and the cetane value of diesel component is higher than 28.

1. the first hydrocarbon fraction derives from brown coal and presses liquefied coal coil or its hydrogenation modification oil, and the first hydrocarbon fraction nitrogen content is lower than 800PPm, and 20 DEG C of density are higher than 960 kilograms/cubic metre;

First hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

In first hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 2PPm; The cetane value of diesel component is higher than 30;

2. the second hydrocarbon fraction derives from brown coal and presses liquefied coal coil or its hydrogenation modification oil, and the second hydrocarbon fraction nitrogen content is lower than 300PPm, and 20 DEG C of density are higher than 930 kilograms of/cubic metre of density;

3rd hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

4th hydrogenation conditions is: pressure is pressure is 10.0 ~ 15.0MPa;

In second hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 2PPm, and the cetane value of diesel component is higher than 30.

Embodiment

Below describe the present invention in detail.

Normal boiling point of the present invention refers to the vapour of material under a barometric point, liquid equilibrium temperature.

The hydro carbons be in a liquid state under conventional liq hydrocarbon of the present invention refers to normal condition, comprises pentane and the higher hydro carbons of boiling point thereof.

Impurity composition of the present invention refers to the hydrogenation products of non-hydrogen in stock oil, non-carbon, comprises water, hydrogen sulfide, ammonia, hydrogenchloride etc.

Proportion of the present invention, unless stated otherwise, refers to the ratio of fluid density and normal pressure under normal pressure, 15.6 DEG C of conditions, 15.6 DEG C of Water Under density.

The composition of component of the present invention or concentration or content value, unless stated otherwise, be weight basis value, weight percent is expressed as m%.

Naphtha Cut of the present invention refers to the hydro carbons that normal boiling point is generally 60 ~ 190 DEG C, is generally 60 ~ 180 DEG C.

Fraction of diesel oil of the present invention refers to the hydro carbons that normal boiling point is generally 160 ~ 390 DEG C, is generally 180 ~ 370 DEG C.

High aromatic hydrocarbons high-density hydrocarbon ils of the present invention, primarily of the hydrocarbon composition that normal boiling point is 165 ~ 450 DEG C, wherein normal boiling point is the weight content of the hydrocarbon of 165 ~ 450 DEG C: be generally greater than 65%, be usually greater than 75%, be greater than 85% especially, its nitrogen content generally lower than 2000PPm, be usually less than 1000PPm, especially lower than 500PPm, 20 DEG C of density generally higher than 920 kilograms/cubic metre, usually above 940 kilograms/cubic metre, especially higher than 960 kilograms/cubic metre, aromaticity content generally higher than 40%, usually above 55%, especially higher than 70%.High aromatic hydrocarbons high-density hydrocarbon oil properties data area of the present invention, is only used to express its hydrogenation characteristic, instead of is used for limiting its physical property or source.The main character of high aromatic hydrocarbons high-density hydrocarbon ils of the present invention is: normal boiling point is that the hydrocarbon being greater than 265 DEG C needs at least to need through unifining process through the hydrocarbon of hydrofining and hydrocracking cascade process, other parts at least partially, the quality index that their the hydrogenation reaction total diesel oil distillate generated in oil just can reach expection as density lower than limits value (such as 20 DEG C of density limits values are 890 kilograms/cubic metre), cetane value higher than limits value (such as 32).

First hydrocarbon fraction of the present invention, its normal boiling point is 265 ~ 450 DEG C, its nitrogen content generally lower than 2000PPm, be usually less than 1000PPm, especially lower than 500PPm, 20 DEG C of density generally higher than 920 kilograms/cubic metre, usually above 940 kilograms/cubic metre, especially higher than 960 kilograms/cubic metre, aromaticity content generally higher than 40%, usually above 55%, especially higher than 70%.First hydrocarbon fraction of the present invention also has the situation exceeding above-mentioned range data.The character data area of the first hydrocarbon fraction of the present invention, is only used to express its hydrogenation characteristic, instead of is used for limiting its physical property or source.The main character of the first hydrocarbon fraction of the present invention is: through hydrofining and hydrocracking cascade process, the quality index that their the hydrogenation reaction total diesel oil distillate generated in oil can reach expection as density lower than limits value (such as 20 DEG C of density limits values are 890 kilograms/cubic metre), cetane value higher than limits value (such as 32).

Second hydrocarbon fraction of the present invention, refer to the hydrocarbon composition that normal boiling point is 165 ~ 265 DEG C, its nitrogen content generally lower than general lower than 800PPm, be usually less than 500PPm, especially lower than 200PPm, 20 DEG C of density generally higher than 900 kilograms/cubic metre, usually above 920 kilograms/cubic metre, especially higher than 940 kilograms/cubic metre, aromaticity content is generally higher than higher than 40%, usually above 55%, especially higher than 70%.Second hydrocarbon fraction of the present invention also has the situation exceeding above-mentioned range data.The character data area of the second hydrocarbon fraction of the present invention, is only used to express its hydrogenation characteristic, instead of is used for limiting its physical property or source.The main character of the second hydrocarbon fraction of the present invention is: through hydrofining or hydrofining and arenes selectivity hydrogenation open loop cascade process, the quality index that their the hydrogenation reaction total diesel oil distillate generated in oil can reach expection as density lower than limits value (such as 20 DEG C of density limits values are 890 kilograms/cubic metre), cetane value higher than limits value (such as 32).

First hydrocarbon fraction hydrogenating reaction effluent of the present invention, refers to the logistics finally entering high pressure separate part in the hydrogenation reaction effluent obtained after the first hydrocarbon fraction completes the hydrogenation process of all series connection.

Second hydrocarbon fraction hydrogenating reaction effluent of the present invention, refers to the logistics finally entering high pressure separate part in the hydrogenation reaction effluent obtained after the second hydrocarbon fraction completes the hydrogenation process of all series connection.

DCL/Direct coal liquefaction process of the present invention, refers to the method being made gelatin liquefaction under solvent oil exists by hydrogenation, according to the difference of solvent oil and catalyzer, pyrolysis way and the difference of hydrogenation mode and the difference of processing condition, can be divided into following several technique:

1. pyrolysis liquefaction process is dissolved: utilize heavy solvent can obtain low-ash extract (Japan claims swelling charcoal) to pyrolysis of coal extracting; Utilize light solvent at supercritical conditions extracting can obtain the oils based on mink cell focus.This method is without hydrogen, though the high product of front a kind of process yield is still solid, rear a kind of technique is as not too high in supercritical extraction (extraction) method (SCE) extract content;

2. solvent hydrogenation extracting liquefaction process: if any solvent refined coal process 1 and II (SRC-1 and SRC-II), Exxon donor solvent process EDS, Japanese New Energy Development Organization liquefaction process (NEDOL) etc., use hydrogen, but pressure is not too high, solvent oil has obvious effect;

3. Hydrogenation method: as the old and new's liquefaction process (IG and NewlG) of Germany and the H-coal process (H-Coal) etc. of the U.S. all belong to this class;

4. coal and residual oil associating processing method (COprocessing): be that solvent oil once passes through reactor, without turning oil together with coal with residual oil.There is hydrocracking simultaneously and be converted into lightweight oil in residual oil.The technique that the U.S., Canada, Germany and USSR (Union of Soviet Socialist Republics) etc. are had nothing in common with each other;

5. destructive distillation liquefaction process: the first pyrolysis of coal obtains tar, then carries out hydrocracking and upgrading to tar;

6. underground liquefaction process: solvent is injected subterranean coal, makes coal depolymerization and dissolving, adds that the surging force of fluid makes coal collapse loose, and not consoluet coal is then suspended in solvent, to be extracted out by solution and be separated processing with pump.

No matter which kind of coal faces hydrogen direct liquefaction process, its target is all obtain oil product, the function pursued is all " coal turns oil ", the chemical transformation that must exist is " coal hydrogenation ", the common trait of this type of technology uses solvent oil and catalyzer at present, the conventional boiling range of solvent oil is generally 200 ~ 450 DEG C, majority is 200 ~ 400 DEG C, and solvent oil majority is distilled oil, and contained aromatic hydrocarbons majority is the aromatic hydrocarbons of 2 ~ 4 ring structures.Therefore, no matter be which kind of coal faces hydrogen direct liquefaction process, the outer oil extraction that its produces or liquefied coal coil (being generally gelatin liquefaction light oil) or liquefied coal coil modified oil, as long as its composition possesses raw material compositing characteristic of the present invention, all can use the inventive method to process.

Below in conjunction with thermally dissolving and catalytic method liquefaction oil and hydrogenation modification oil description the present invention thereof of brown coal preparing liquid fuel.

The thermally dissolving and catalytic method liquefaction oil of high aromatic hydrocarbons high-density hydrocarbon ils of the present invention such as brown coal preparing liquid fuel and hydrogenation modification oil thereof, be generally high-density hydrocarbon ils after hydrogenation, can be hydrogenation modification oil or liquefied coal coil or their mixing oil of liquefied coal coil, usually comprising conventional boiling range is 165 ~ 450 DEG C of hydrocarbon components, be characterized in containing different boiling ranges fraction (such as naphtha Cut, fraction of diesel oil, heavy fraction) and the conventional boiling range usually comprising 20 ~ 65% is 160 ~ 265 DEG C of hydrocarbon components, character (the such as hydrogen richness of different boiling ranges fraction, density, viscosity, residual carbon content, metal content, oxygen level, sulphur content, nitrogen content, two ring aromatic content, polycyclic aromatic hydrocarbon content, boiling point) difference is very large.

Owing to originating, difference and source process condition change all within the specific limits, and described high aromatic hydrocarbons high-density hydrocarbon oil properties of the present invention also changes within the specific limits.For the thermally dissolving and catalytic method liquefaction oil of brown coal preparing liquid fuel and hydrogenation modification oil thereof, after hydrogenation of the present invention, high-density hydrocarbon oil properties proportion is generally 0.90 ~ 1.04, normal boiling point is generally 60 ~ 480 DEG C and is generally 165 ~ 450 DEG C, and usual metal content is 0 ~ 10PPm, sulphur content is 0 ~ 0.06%, nitrogen content is 0.005 ~ 0.20%, total aromaticity content is 35 ~ 85%, two ring aromatic content is 25 ~ 70%, thrcylic aromatic hydrocarbon content is 5 ~ 45%.

According to the present invention, after described hydrogenation, high-density hydrocarbon ils is usually from hydrogenation process, therefore usually metal content and solid content very low.According to the present invention, after described hydrogenation, high-density hydrocarbon ils is usually from the hydrogenation process producing hydrogen sulfide and ammonia, because ammonia process is washed in the water filling of hydrogenation process experience, after producing hydrogenation, the hydrogenation process reaction of high-density hydrocarbon ils generates oil (high score oil) usually containing moisture.After typical hydrogenation, high-density hydrocarbon ils character is in table 1.

For the thermally dissolving and catalytic method liquefaction oil of brown coal preparing liquid fuel and hydrogenation modification oil thereof, first hydrocarbon fraction of the present invention, primarily of the high aromatic hydrocarbons high-density last running composition that normal boiling point is 265 ~ 450 DEG C, it can be from tank field, also can be the fraction that initial high aromatic hydrocarbons high-density hydrocarbon ils separate part obtains, it can be such as the distillate that gelatin liquefaction generates the fractionating section generation of the hydrogenation modification oil of oil, mainly comprise conventional boiling range and be generally 265 ~ 450 DEG C, be generally the hydrocarbon component of 265 ~ 420 DEG C, its acenaphthene class, acenaphthylene class, thrcylic aromatic hydrocarbon content is higher (is generally 10 ~ 30%, be generally 15 ~ 25%).

For the thermally dissolving and catalytic method liquefaction oil of brown coal preparing liquid fuel and hydrogenation modification oil thereof, second hydrocarbon fraction of the present invention, primarily of the high aromatic hydrocarbons high-density lighting end composition that normal boiling point is 165 ~ 265 DEG C, it can be from tank field, also can be the fraction that initial high aromatic hydrocarbons high-density hydrocarbon ils separate part obtains, it can be such as the distillate that gelatin liquefaction generates the fractionating section generation of the hydrogenation modification oil of oil, mainly comprise conventional boiling range and be generally 60 ~ 265 DEG C, be generally the hydrocarbon component of 165 ~ 265 DEG C, its two ring aromatic content is higher (is generally 20 ~ 80%, be generally 30 ~ 65%).

Characteristic of the present invention is below described.

Operational condition of the present invention is generally:

First hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

3rd hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

First hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

3rd hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

4th hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

The present invention is suitable for processing following oil product:

First hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

2. the second hydrocarbon fraction derives from brown coal and presses liquefied coal coil or its hydrogenation modification oil, and the second hydrocarbon fraction nitrogen content is lower than 300PPm, and 20 DEG C of density are higher than 930 kilograms/cubic metre;

3rd hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

4th hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

Below describe each step of the present invention in detail.

Below describe the first hydrogenation reaction part of the present invention in detail.

In the first hydrogenation reaction part, under the first hydrogenation catalyst existence condition, described first hydrocarbon fraction completes the first hydrogenation reaction, generates first hydrogenation reaction effluent be made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.

First hydrogenation reaction of the present invention, be commonly referred to as the reaction process of the consumption hydrogen that the first hydrocarbon fraction occurs under hydrogen and suitable the first hydrogenation catalyst (Hydrobon catalyst) existence condition, its minimum reaction depth should possess MIN industrial significance: the hydrofining namely the first hydrocarbon fraction being completed to expection, the first hydrogenation reaction degree of depth should be determined ingredient requirement according to the first hydrocarbon fraction character and the second hydrogenation process, the nitrogen content (mean value) of the first hydrogenation process gained hydrogenated oil is usually less than 50PPm, should lower than 30PPm, be preferably lower than 15PPm, in this process, the aromatic hydrogenation saturated reaction transformation efficiency of the first hydrocarbon fraction is usually above 40%, the aromaticity content (mean value) of gained hydrogenated oil is lower than 45%, should lower than 35%, be preferably lower than 25%, to be suitable for making hydrocracking process (the second hydrogenation process) stock oil.

The first described hydrogenation reaction part, because of the difference of the first hydrocarbon fraction character (metal content, oxygen level content, olefin(e) centent, sulphur content, nitrogen content, aromaticity content, boiling range, proportion) and the difference of the first hydrogenation reaction (hydrogenation deoxidation, hydrogenating desulfurization, hydrodenitrification, the hydrotreated lube base oil) degree of depth, the variation range of its operational condition is very wide, should determine according to concrete process condition.

Described first hydrogenation reaction part, the first hydrogenation catalyst of use can be the series combination of one or two or more Hydrobon catalyst and load in mixture.First hydrogenation catalyst, can be the special-purpose catalyst for concrete raw material, also can be the Hydrobon catalyst with hydrodemetallation (HDM) or hydrogenation deoxidation or hydrogenating desulfurization or the function such as hydrodenitrification or hydrotreated lube base oil and the combination thereof of the unifining process use of suitable refining of petroleum heavy gas oil type or wax oil type.

Any one supplementary sulphur can be added the first hydrogenation reaction part as required, to ensure minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v) that reactive moieties is necessary, to ensure that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value.Described supplementary sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide to the material of hydroconversion process without undesirable action, such as hydrogen sulfide containing gas or oil product, or generate the dithiocarbonic anhydride of hydrogen sulfide or Methyl disulfide etc. after contacting with high-temperature hydrogen.

First hydrogenation reaction part and the second hydrogenation reaction part, should treat as a complete operation, therefore, the first hydrogenation reaction part can regard the pre-hydrogenation process of the second hydrogenation reaction part as.

Below describe the second hydrogenation reaction part of the present invention in detail.

Second hydrogenation reaction of the present invention, be commonly referred to as the reaction process of the consumption hydrogen that hydrocarbon fraction occurs in the first hydrogenation reaction effluent under hydrogen and suitable the second hydrogenation catalyst (hydrocracking catalyst) existence condition, its minimum cracking reaction degree of depth should possess MIN industrial significance: the hydrocracking namely completing expection, the nitrogen content (mean value) of this process gained hydrotreated naphtha lower than 10PPm, should lower than 4PPm, be preferably lower than 2PPm, to be suitable for doing Naphtha reformer feed blend component; The cetane value (mean value) of this process gained hydrogenated diesel oil generally higher than 30, usually above 35, better for 40.In this process, in the first hydrogenation reaction effluent, the hydrocracking cracking rate of hydrocarbon fraction is determined on a case-by-case basis, and 20 DEG C of density of 20 DEG C of density ratio first hydrocarbon fractions of the diesel component in the second hydrogenation reaction effluent reduce by 30 ~ 100kg/ cubic meter.

In the second hydrogenation reaction part, under hydrocracking catalyst existence condition, the fraction of hydrocarbon at least partially in first hydrogenation reaction effluent and hydrogen complete hydrocracking reaction, generate one and form the second hydrogenation reaction effluent by hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.

Described second hydrogenation reaction part, because of the difference of the difference of its raw material (the hydrocarbon fraction in the first hydrogenation reaction effluent) character (nitrogen content, aromaticity content, density) and the hydrocracking reaction degree of depth of expection, the variation range of its operational condition is very wide, should determine according to concrete process condition.

The hydrocracking catalyst that second hydrogenation reaction part uses can be the series combination of one or two or more catalyzer and load in mixture.Hydrocracking catalyst can be the catalyzer for concrete raw material, also can be hydrocracking catalyst (comprise and relax cracking catalyst) and the combination thereof of the hydrocracking process use of suitable petroleum refining process poor ignition quality fuel and/or wax oil/or heavy oil.

Second hydrogenation reaction part, amorphous (sial) hydrocracking catalyst of amorphous (sial) hydrocracking catalyst of not fusion molecular sieve or a small amount of fusion molecular sieve can be selected, to strengthen the adaptive faculty to organic nitrogen compound in raw material as far as possible, improve diesel component productive rate.Second hydrogenation reaction part also can use hydrocracking catalyst and rear portion Hydrobon catalyst to carry out grating, and the mercaptan that rear portion Hydrobon catalyst is used for cracking process produces is converted into the objects such as hydrogen sulfide.

Hydrocracking reaction one word of the second hydrogenation reaction part, refer under hydrogen and suitable catalyzer existence condition, the reaction process (usually comprising cracking reaction) of the consumption hydrogen that Hydrocracking Raw Oil occurs, its minimum reaction depth should possess MIN industrial significance: the fraction of diesel oil such as producing expection character, should according to hydrocracking reaction part material oil nature, expection fraction of diesel oil character and hydrocracking catalyst performance are determined: to improving fraction of diesel oil cetane value, reduce fraction of diesel oil density to re-set target, take into account liquid yield simultaneously, this process cracking conversion rate is generally 15 ~ 70%, be generally 25 ~ 55%.

Below describe the 3rd hydrogenation reaction part of the present invention in detail.

In the 3rd hydrogenation reaction part, under the 3rd hydrogenation catalyst existence condition, described second hydrocarbon fraction and hydrogen complete the 3rd hydrogenation reaction, generate the 3rd hydrogenation reaction effluent be made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.

3rd hydrogenation reaction of the present invention, be commonly referred to as the hydrofining reaction of the consumption hydrogen that the second hydrocarbon fraction occurs under hydrogen and suitable catalyzer existence condition, its minimum reaction depth should possess MIN industrial significance: the hydrofining namely the second hydrocarbon fraction being completed to expection, the 3rd hydrogenation reaction degree of depth should be determined according to the second hydrocarbon fraction character and hydrogenation target call, the nitrogen content (mean value) of this process gained hydrogenated oil is lower than 50PPm, should lower than 30PPm, be preferably lower than 15PPm, in this process, the saturated transformation efficiency of aromatic hydrogenation of the second hydrocarbon fraction is usually above 40%, the aromaticity content (mean value) of gained hydrogenated oil is lower than 45%, should lower than 35%, be preferably lower than 25%, the cetane value (mean value) of this process gained hydrogenated diesel oil is general higher than 26, usually above 28, the nitrogen content (mean value) of this process gained hydrotreated naphtha lower than 10PPm, should lower than 4PPm, be preferably lower than 2PPm, to be suitable for doing Naphtha reformer feed blend component.

The 3rd described hydrogenation reaction part, because of the difference of the second hydrocarbon fraction character (metal content, oxygen level, sulphur content, nitrogen content, aromaticity content, boiling range, proportion) and the difference of the 3rd hydrogenation reaction (hydrogenation deoxidation, hydrogenating desulfurization, hydrodenitrification, the hydrotreated lube base oil) degree of depth, the variation range of its operational condition is very wide, should determine according to concrete process condition.

Described 3rd hydrogenation reaction part, the 3rd hydrogenation catalyst of use can be the series combination of one or two or more catalyzer and load in mixture.3rd hydrogenation catalyst can be the Special hydrogenation catalyst for refining for concrete raw material.Also can be Hydrobon catalyst and the combination thereof of the hydrodemetallation (HDM) that uses of suitable refining of petroleum diesel oil hydrofining process or hydrogenation deoxidation or hydrogenating desulfurization or the function such as hydrodenitrification or hydrotreated lube base oil.

Described 3rd hydrogenation reaction part, any one supplementary sulphur can be added reactive moieties as required, to ensure minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v) that reactive moieties is necessary, to ensure that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value.Described supplementary sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide to the material of hydroconversion process without undesirable action, such as hydrogen sulfide containing gas or oil product, or after contacting with high-temperature hydrogen, be converted into the dithiocarbonic anhydride or Methyl disulfide etc. of hydrogen sulfide.

Below describe the 4th hydrogenation reaction part of the present invention in detail.

When existence the 4th hydrogenation reaction part, in this process general, in the 3rd hydrogenation reaction effluent, hydrocarbon fraction completes twin nuclei hydrocarbon hydrogenation ring-opening reaction, its minimum reaction depth should possess MIN industrial significance: the nitrogen content (mean value) of this process gained hydrotreated naphtha lower than 4PPm, should lower than 2PPm, be preferably lower than 1PPm, to be suitable for doing Naphtha reformer feed blend component; The cetane value (mean value) of this process gained hydrogenated diesel oil is generally higher than 30, usually above 32, preferably is higher than 35; In this process, the transformation efficiency of twin nuclei aromatic hydrogenation cracking reaction is generally higher than 40%, usually above 50%, preferably is higher than 60%.

When existence the 4th hydrogenation reaction part, the 3rd hydrogenation reaction part and the 4th hydrogenation reaction part, should treat as a complete operation, now, the 3rd hydrogenation reaction part can regard the pre-hydrogenation process of the 4th hydrogenation reaction part as.

Below describe the 4th hydrogenation catalyst of the present invention in detail.

4th hydrogenation catalyst, preferably possess double ring arene or dicyclo naphthenic hydrocarbon selective hydrogenation open loop function, it can be any one suitable diesel oil selective hydrogenation ring opening catalyst, it can be typical petroleum base height two ring aromatic content catalytic diesel oil selective hydrogenation open loop dearomatization catalyst, these technology have the MCI technology of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute, the RICH technology etc. of Beijing Research Institute of Petro-Chemical Engineering of Sinopec Group, record the document of this kind of technology in table 3.The lysate diesel yield of diesel component in 4th hydrogenation reaction part hydrocarbon oil crude material: be generally greater than 85%, be usually greater than 90%, more preferably greater than 95%.

According to the present invention, 4th hydrogenation catalyst can be the hydrocracking catalyst that any one is suitable, can be such as the catalyzer identical with the second hydrogenation catalyst that the second hydrogenation reaction part uses but its service temperature, liquid hourly space velocity differ larger: higher such as high by more than 30%, the service temperature of usual 4th hydrogenation catalyst liquid hourly space velocity is lower such as low 15 ~ 30 DEG C.

The publication of arenes selectivity hydrogenation ring opening catalyst recorded by table 3

According to the present invention, use the second hydrogenation catalyst 2R1C (hydrocracking catalyst) to carry out hydrocracking in the second hydrogenation reaction part and produce diesel oil, but do not get rid of contact arenes selectivity hydrogenation ring opening catalyst 2R2C after under the condition formerly contacting hydrocracking catalyst 2R1C, this is because diesel component content is high in the product 2R1P of high-density heavy fraction contact hydrocracking catalyst 2R1C generation, the dicyclo naphthenic hydrocarbon that 2R1P contains and double ring arene can improve quality after contacting arenes selectivity hydrogenation ring opening catalyst 2R2C and (under the condition that gas yield is low, improve cetane value, reduce density), therefore suitably can reduce the consumption of hydrocracking catalyst 2R1C or enter by the hydrogenated oil heavy bavin component circulation of setting up the second hydrogenation reaction part the circulation hydrocracking flow process that the second hydrogenation reaction part contact 2R2C forms low gas yield.Recycle stream can be the narrow fraction oil (being generally boiling point soprano) formed primarily of high-density component primarily of hot high score oil or the high score oil separation section gained of high-density component composition that the second hydrogenation reaction effluent special hot high score produces, there is hydrocarbon ils circulation process in now the present invention, recycle stream enters the second hydrogenation reaction part after can entering the first hydrogenation reaction part, recycle stream also directly can enter the second hydrogenation reaction part and contact with the second hydrogenation catalyst of optional position, certainly can be that recycle stream directly enters the second hydrogenation reaction part and contacts with arenes selectivity hydrogenation ring opening catalyst 2R2C.

Enter high pressure separate part after first hydrocarbon fraction hydrogenating reaction effluent and the second hydrocarbon fraction hydrogenating reaction effluent mix usually, at high pressure separate part, complete separation and obtain high score gas, high score oil and high score water; High score gas enters hydrogenation reaction part and does recycle hydrogen use at least partially.

Below describe high pressure separate part of the present invention in detail.

First hydrocarbon fraction hydrogenating reaction effluent and the second hydrocarbon fraction hydrogenating reaction effluent inject washing water before entering high pressure separate part usually in hydrogenation reaction effluent.Described hydrogenation reaction effluent first reduces temperature (being generally and reactive moieties charging heat exchange) usually to about 220 ~ 100 DEG C (these temperature should higher than sulphur hydrogenation ammonia Tc in hydrogenation reaction effluent gas phase), is then mixed to form water filling back end hydrogenation reaction effluent with the washing water added.Washing water are for absorbing ammonia in hydrogenation reaction effluent and other impurity issuable as hydrogenchloride etc., and the aqueous solution after absorbing ammonia must absorb the hydrogen sulfide in hydrogenation reaction effluent.

Described high pressure separate part comprises cooling, the separating step of water filling back end hydrogenation reaction effluent.At this, described water filling back end hydrogenation reaction effluent first reduces temperature (usually using air-cooler and or watercooler) usually to about 30 ~ 70 DEG C.

At high pressure separate part, described water filling back end hydrogenation reaction effluent is separated into: one on volume primarily of the high score gas of hydrogen composition, high score oil primarily of conventional liq hydrocarbon and dissolved hydrogen composition, one primarily of water composition and be dissolved with the high score water of hydrogen sulfide, ammonia.Described high score water, wherein the content of ammonia is generally 0.5 ~ 15% (w), is preferably 1 ~ 8% (w).An object of note washing water absorbs ammonia in hydrogenation reaction effluent and hydrogen sulfide, prevents the hydrogenation reaction effluent process that cools from forming sulphur hydrogenation ammonia or many sulphur ammonia Crystallization Plugging heat exchanger channel, increase system pressure drop.

The injection rate of described washing water, should determine according to following principle: on the one hand, and washing water are divided into vapour phase water and liquid phase water after injecting hydrogenation reaction effluent, and the liquid phase water yield must be greater than zero, is preferably 30% of washing water total amount or more; Again on the one hand, washing water, for absorbing the ammonia in hydrogenation reaction effluent, prevent the ammonia density of high score gas too high, reduce catalyst activity, the ammonia volumetric concentration of usual high score gas is more low better, is generally not more than 200PPm (v), is preferably not more than 50PPm (v).

Described high pressure separate part, its separator operation pressure is that hydrogenation reaction partial pressure deducts true pressure and falls, and the difference of high pressure separate part working pressure and hydrogenation reaction pressure is unsuitable too low or too high, is generally 0.5 ~ 1.2MPa.

Described high score gas, its hydrogen volume concentration value, should not too low (causing device working pressure to rise), generally should be not less than 70% (v), should be not less than 80% (v), preferably be not less than 85% (v).

As previously mentioned at least partially, the high score gas being generally 85 ~ 100% returns hydrogenation reaction part formation recycle hydrogen, with the amounts of hydrogen providing hydrogenation reaction part necessary and hydrogen concentration; In order to improve plant investment efficiency, must ensure that recycle hydrogen concentration is not less than aforesaid low limit value, for this reason, according to concrete feedstock property, reaction conditions, product slates, a part of described high score gas (hereinafter referred to as discharge gas) can be got rid of to get rid of methane, ethane that reaction produces.For discharge gas, conventional membrane separation process or pressure swing adsorption technique or oil wash technique can be adopted to realize hydrogen and non-hydrogen gas Component seperation, and the hydrogen reclaimed is used as new hydrogen.

Before high pressure separate part, thermal high separate part can be set.

Before first hydrocarbon fraction hydrogenating reaction effluent enters high pressure separate part, special thermal high separate part AHPS can be set.

New hydrogen enters and adds hydrogen partial to supplement the hydrogen adding hydrogen partial and consume, and new hydrogen hydrogen concentration is more high better, generally lower than 95% (v), preferably should not be not less than 99% (v).Whole new hydrogen can be introduced arbitrary hydrogenation reaction part.

Below describe high score oil separation section of the present invention in detail.

High score oil separation section described herein, refers to step high score fluid body being separated into narrow fraction oil production, and its liquid product comprises primarily of the hydrocarbon ils of normal boiling point higher than the component composition of 50 DEG C.At this, first described high score oil reduce pressure, usually Pressure Drop to 0.5 ~ 4.0MPa and form gas, the logistics of liquid mixed phase, then through separation with or the process of fractionation complete and be separated, be usually separated into gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil (or hydrogenation solar oil and hydrogenation heavy gas oil), hydrogenation heavy oil etc.

The typical hydroconversion process of the present invention can metal, oxygen, sulphur, nitrogen in effective elimination raw material, make wherein saturated, the cracking of ring compound at least partially, oil property is significantly improved, usual naphtha Cut product can as high-quality catalytic reforming raw material component, fraction of diesel oil product can as fine-quality diesel oil blending component.The operational condition of each hydrogenation reaction part, generally should reach following effect: in the hydrogenated oil that high pressure separate part is discharged, the nitrogen content (mean value) of hydrotreated naphtha general lower than 4PPm, be usually less than 2PPm, be preferably lower than 1PPm; The cetane value (mean value) of hydrogenated diesel oil is higher than 30, preferably higher than 35.

In order to improve the first hydrogenation reaction part material oil nature, delay coking speed, prolong operation cycle, simultaneously in order to suitably reduce the second hydrogenation reaction partial hydrogenation cracking per pass conversion (reduction gas yield), when the present invention is applied to the first hydrocarbon fraction hydrogenating conversion, the 3rd raw material hydrocarbon can be processed.3rd raw material hydrocarbon can be any one suitable hydrocarbon, can be petroleum base hydrocarbon or shale oil base hydrocarbon or coal-tar base hydrocarbon, 3rd raw material hydrocarbon also can be the narrow fraction oil (being generally boiling point soprano) primarily of high-density component composition obtained primarily of hot high score oil or the high score oil separation section of high-density component composition that hydrocarbonaceous stream such as the second hydrogenation reaction effluent special hot high score produced from the first hydrocarbon fraction hydrogenating cracking process produces, there is hydrocarbon ils circulation process in now the present invention, recycle stream enters the second hydrogenation reaction part after can entering the first hydrogenation reaction part, recycle stream also directly can enter the second hydrogenation reaction part and contact with the second hydrogenation catalyst of optional position.Using the 3rd suitable raw material hydrocarbon, by improving the character of the first hydrogenation reaction sub-population raw material, the operational condition of the first hydrogenation reaction part, the second hydrogenation reaction part can be improved.In order to obtain best effect, the normal boiling point initial boiling point of the 3rd raw material hydrocarbon, generally higher than the normal boiling point initial boiling point of the first hydrocarbon fraction, when the 3rd raw material hydrocarbon is outside from flow process of the present invention, 20 DEG C of density are preferably higher than 920 kilograms/cubic metre, and when the 3rd raw material hydrocarbon is inner from flow process of the present invention, 20 DEG C of density are preferably higher than 900 kilograms/cubic metre.

When the 3rd raw material hydrocarbon is the hot high score oil primarily of high-density component composition from the second hydrogenation reaction effluent special hot high score generation, there is " short circulation cracking flow process " in now the present invention: the second hydrogenation reaction effluent enters thermal high separate part AHPS and is separated into one on volume primarily of the first hydrocarbon fraction hydrogenating series of heat high score gas gas of hydrogen composition and a first hydrocarbon fraction hydrogenating series of heat high score fluid body containing dissolved hydrogen primarily of conventional liq hydrocarbon composition.High pressure separate part is entered after first hydrocarbon fraction hydrogenating series of heat high score gas and the mixing of the second hydrocarbon fraction hydrogenating reaction effluent.Cycling hot high score oil RHPO enters the second hydrogenation reaction part and contacts with the second hydrogenation catalyst, by increasing cycling hot high score oil RHPO quantity, reduce the second hydrogenation reaction part cracking per pass, temperature of reaction can be reduced, delay catalyzer coking, reduce gas yield, reduce hydrogen consumption, increase diesel yield.

The macromole cracking that first hydrocarbon fraction occurs at hydrocracking process (the second hydrogenation reaction part) can produce sulfur-bearing, nitrogenous petroleum naphtha component, in order to improve the second hydrogenation reaction effluent or the second hydrogenation reaction effluent further hot high score gas in the quality of oil product (petroleum naphtha component), heavy fractioning hydrogenation series of heat high score gas can be introduced afterbody hydrogenation reaction part, also the second hydrocarbon fraction hydrogenating reaction effluent can be introduced afterbody hydrogenation reaction part simultaneously, use Hydrobon catalyst to carry out hydrofining to hydrocarbon component and (such as reduce petroleum naphtha component nitrogen content and sulphur content, reduce diesel component aromaticity content), afterbody hydrogenation reaction effluent enters high pressure separate part.

In order to the hydrogenation modification process gained naphtha fraction processed from liquefied coal coil is suitable for being used as the high-quality feed naphtha of catalytic reforming aromatic hydrocarbons to obtain, the 4th hydrocarbon feed can be it can be used as to introduce the 3rd hydrogenation reaction part, possess improvement the 3rd hydrogenation reaction part material oil nature simultaneously, delay the effect of coking speed, prolong operation cycle.4th raw material hydrocarbon can be any one suitable hydrocarbon, can be petroleum base hydrocarbon or shale oil base hydrocarbon or coal-tar base hydrocarbon, 4th raw material hydrocarbon also can be from second hydrocarbon fraction hydrogenating process produce hydrocarbonaceous stream such as high score oil separation section obtain primarily of naphtha fraction and or solar oil fractions consisting narrow fraction oil, there is lighter hydrocarbons recycle stream in now the present invention, lighter hydrocarbons recycle stream enters the 4th hydrogenation reaction part after can entering the 3rd hydrogenation reaction part, lighter hydrocarbons recycle stream also directly can enter the 4th hydrogenation reaction part and contact with the second hydrogenation catalyst of optional position.Using the 4th suitable raw material hydrocarbon, by improving the character of the 3rd hydrogenation reaction sub-population raw material, the operational condition of the 3rd hydrogenation reaction part, the 4th hydrogenation reaction part can be improved.In order to obtain best effect, the conventional boiling range of the 4th raw material hydrocarbon is preferably in the conventional boiling point range of the second raw material hydrocarbon.

When the 4th raw material hydrocarbon is the second hydrocarbon fraction hydrogenating reaction effluent hot high score oil produced from the second hydrocarbon fraction hydrogenating reaction effluent special hot high score, there is " light oil short circuit current journey " in now the present invention: the second hydrocarbon fraction hydrogenating reaction effluent enters thermal high separate part LAHPS and is separated into one on volume primarily of the second hydrocarbon fraction hydrogenating series of heat high score gas gas of hydrogen composition and a second hydrocarbon fraction hydrogenating series of heat high score fluid body LHPO containing dissolved hydrogen primarily of conventional liq hydrocarbon composition.High pressure separate part is entered after second hydrocarbon fraction hydrogenating series of heat high score gas and the mixing of the first hydrocarbon fraction hydrogenating reaction effluent.Cycling hot high score oil RLHPO enters the 3rd hydrogenation reaction part and contacts with the 3rd hydrogenation catalyst, by increasing cycling hot high score oil RLHPO quantity, reduce the 3rd hydrogenation reaction part material aromaticity content, temperature of reaction can be reduced, delay catalyzer coking, prolong operation cycle.

The invention has the advantages that:

1. to the fraction of different boiling ranges, select hydrogenation conditions suitable separately, can improve the quality of products, quiet run, raising liquid product yield, reduce catalyst levels, avoid excessive hydrogen consume, save be separated power consumption, therefore the present invention be suitable for wide fraction high aromatic oil classification Unionfining transform;

2. reaction effluent combined separation, can simple flow;

3. hydrogenation heavy gas oil fraction is introduced the 4th hydrogenation reaction part, high diesel yield hydro-upgrading is carried out to it, realize fractionation and circulating reaction coupling optimization;

4. high-density fraction after part or all of hydrogenation is introduced the second hydrogenation reaction part, component part circulation or all circulation cracking flow process, realize fractionation and circulating reaction coupling optimization;

5. high-density fraction after part or all of hydrogenation is incorporated into the second hydrogenation reaction part to contact with latter half cracking catalyst (not contacting with first half cracking catalyst), component part circulation or all circulation relax cracking flow process, realize fractionation and circulating reaction coupling is optimized, after the first hydrocarbon fraction and hydrogenation, high-density fraction achieves differentiation at the per pass conversion of the second hydrogenation reaction part;

6. device smooth operation of the present invention is adopted;

7. device emergency shutdown process safety of the present invention is adopted;

8. the present invention is suitable for new device or existing plant modification.

Embodiment one

The hydroconversion process of the outer oil extraction of certain brown coal medium-pressure hydrocracking direct liquefaction process adopts the present invention, and its major objective produces fine-quality diesel oil cut.

The outer oil extraction oil product C listed by table 1 of coal liquifaction process, its normal boiling point accounts for 40% lower than the component of 265 DEG C, adopt the present invention, underpressure distillation is completed to it and is separated (completing dehydration) simultaneously, reboiler furnace at the bottom of separation column tower (also can establish separation column charging process furnace) is set, fractionator overhead pressure is ~ 0.05MPa (absolute pressure), separation column hypomere is stripping section, separation column epimere is rectifying section, all outer oil extraction is separated into oil (normal boiling point 265 ~ 390 DEG C) at the bottom of the tower of discharge at the bottom of the overhead oil (normal boiling point is lower than 265 DEG C) and tower that return tank of top of the tower discharges.At the bottom of tower, oil is as the first hydrocarbon fraction, and overhead oil is as the second hydrocarbon fraction, and the present invention's each step operational condition is as follows:

1. the first hydrocarbon fraction is the component composition of 265 ~ 390 DEG C primarily of normal boiling point, in the first hydrogenation reaction part, first hydrocarbon fraction complete saturated transformation efficiency be ~ 65% aromatic hydrogenation saturated reaction be converted into the first hydrogenation reaction effluent, the first hydrogenation conditions is: temperature is 340 ~ 400 DEG C, pressure is 11.0 ~ 13.0MPa, the first hydrogenation catalyst volume space velocity is 0.35 ~ 0.40hr ^-1, hydrogen/stock oil volume ratio is 1000: 1 ~ 1200: 1, arranges multiple beds;

In the second hydrogenation reaction part, the hydrocracking reaction that first hydrogenation reaction effluent completes expection is converted into the second hydrogenation reaction effluent, and the second hydrogenation conditions is: temperature is 350 ~ 400 DEG C, pressure is 11.0 ~ 13.0MPa, the second hydrogenation catalyst possesses gas yield is low and diesel yield is high function, the second hydrogenation catalyst volume space velocity is about 0.5 ~ 0.55hr ^-1, hydrogen/stock oil volume ratio for being not less than 1200: 1, multiple beds is set; Second hydrogenation reaction effluent is used as the first hydrocarbon fraction hydrogenating reaction effluent;

In first hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is 33 ~ 38 (it is more than 33 that the present embodiment controls) lower than the cetane value of 2PPm (the present embodiment controls as below 1PPm), diesel component;

2. the second hydrocarbon fraction is primarily of the component composition of normal boiling point lower than 265 DEG C, account for the 40m% of outer oil extraction, in the 3rd hydrogenation reaction part, second hydrocarbon fraction complete saturated transformation efficiency be ~ 70% aromatic hydrogenation saturated reaction be converted into the 3rd hydrogenation reaction effluent, the 3rd hydrogenation conditions is: temperature is 310 ~ 380 DEG C, pressure is 11.0 ~ 13.0MPa, the 3rd hydrogenation catalyst volume space velocity is 0.50 ~ 0.55hr ^-1, hydrogen/stock oil volume ratio is 800: 1 ~ 1000: 1, arranges multiple beds;

In the 4th hydrogenation reaction part, 3rd hydrogenation reaction effluent complete double ring arene open loop rate be ~ 80% highly selective double ring arene hydrogenation ring-opening reaction be converted into the 4th hydrogenation reaction effluent, the 4th hydrogenation conditions is: temperature is 330 ~ 390 DEG C, pressure is 11.0 ~ 13.0MPa, the 4th hydrogenation catalyst possesses highly selective double ring arene hydrogenation open loop function, the 4th hydrogenation catalyst volume space velocity is 0.5 ~ 1.0hr ^-1, hydrogen/stock oil volume ratio is not less than 1200: 1, arranges multiple beds; 4th hydrogenation reaction effluent is used as the second hydrocarbon fraction hydrogenating reaction effluent;

In second hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is 33 ~ 38 (it is more than 33 that the present embodiment controls) lower than the cetane value of 2PPm (the present embodiment controls as below 1PPm), diesel component;

3. heat exchange temperature-fall period is completed after the first hydrocarbon fraction hydrogenating reaction effluent and the mixing of the second hydrocarbon fraction hydrogenating reaction effluent, then high pressure separate part is entered after injecting wash-down water, be separated into high score gas, high score oil and high score water, the high-pressure separator operational condition of high pressure separate part is: temperature is 45 ~ 55 DEG C, pressure is 10.5 ~ 12.5MPa;

4. all high score gas enters each hydrogenation reaction part and makes reactor inlet hydrogen and catalyst bed interlayer quenching hydrogen; New hydrogen from outside fills into reaction under high pressure system;

5. in high score oil separation section, be separated high score oil and obtain following hydrogenation oil product: conventional boiling range is the petroleum naphtha of 50 ~ 165 DEG C, conventional boiling range is the solar oil cut of 165 ~ 265 DEG C and conventional boiling range is the heavy gas oil cut (20 DEG C of density are about 0.895) of 265 ~ 330 DEG C, the heavy gas oil cut of 10 ~ 50% can be recycled to the first hydrogenation reaction part or be recycled directly to the second hydrogenation reaction part.

The hydrogenation catalyst composition used is in table 4 ~ table 7, and technical solution of the present invention achieves production object: the nitrogen content of hydrogenation upgrading petroleum naphtha component is 33 ~ 38 (it is more than 33 that the present embodiment controls) lower than 2PPm (the present embodiment controls as below 1PPm), all cetane value (mean value) of hydrogenation upgrading fraction of diesel oil.

Table 4 first hydrogenation reaction part catalyzer forms

The physico-chemical property of table 5 second hydrogenation reaction part catalyzer

Table 6 the 3rd hydrogenation reaction part catalyzer forms

Table 7 the 4th hydrogenation reaction part catalyzer

The present embodiment one, conventional gas Auditory steady-state responses is 3.2 ~ 3.5% (relative to hydrogenating materials weight of oils), naphtha yield is 9.1 ~ 10.0% (relative to hydrogenating materials weight of oils), diesel yield is 90.2 ~ 91.0% (relative to hydrogenating materials weight of oils), and unit weight stock oil hydrogen consumption is 3.32 ~ 3.45% (relative to hydrogenating materials weight of oils).

Table 8 hydrogenated products oil property

The advantage of embodiment is:

1. the first hydrogenation reaction part of the first hydrocarbon fraction, uses Hydrodemetalation catalyst and the hydrofining agent with excellent aromatic saturation function; Second hydrogenation reaction part, uses and possesses the amorphous aluminum silicide hydrocracking catalyst that gas yield is low and diesel yield is high;

3rd hydrogenation reaction part of the second hydrocarbon fraction, uses protective material and the hydrofining agent (being different from the first hydrogenation reaction part hydrofining agent) with excellent aromatic saturation function; 4th hydrogenation reaction part uses highly selective double ring arene hydrogenation ring opening catalyst;

2. the 3rd hydrogenation reaction part is compared with the first hydrogenation reaction part, initial reaction temperature differs from 30 DEG C, select respective suitable temperature of reaction, avoid fraction of diesel oil excessive hydrogenation, reduce hydrogen consumption, increase liquid product yield, ensure that simultaneously the nitrogen content of hydrogenation upgrading petroleum naphtha component lower than 2PPm, hydrogenation upgrading fraction of diesel oil cetane value (mean value) higher than 33 target;

4th hydrogenation reaction part is compared with the second hydrogenation reaction part, initial reaction temperature differs from 20 DEG C, respective suitable temperature of reaction and catalyzer are selected, avoid fraction of diesel oil excessive hydrogenation, reduce hydrogen consumption, increase liquid product yield, ensure that simultaneously the cetane value (mean value) of hydrogenation upgrading fraction of diesel oil higher than 33 target;

3. the heavy gas oil cut of 10 ~ 50% can be recycled to the first hydrogenation reaction part or be recycled directly to the second hydrogenation reaction part, specific aim can improve the first hydrogenation reaction part material oil nature, form heavy gas oil circulation hydrocracking flow process simultaneously, suitably can reduce the second hydrogenation reaction part oil product cracking per pass, reduce gas yield;

4. heat exchange temperature-fall period is completed after reaction effluent and the mixing of the second hydrocarbon fraction hydrogenating reaction effluent, then high pressure separate part is entered after injecting wash-down water, be separated into high score gas, high score oil and high score water, hydrogenation reaction component loops hydrogen common recycle hydrogen compressor, achieve raw material classification Unionfining to transform, simplify flow process, significantly reduce investment outlay;

5. classification process raw material oil improve diesel yield: on the one hand, lighting end (the second hydrocarbon fraction) without the second hydrogenation process (hydrocracked, treated process), can avoid overcracking, reduce gas yield; On the other hand, consider cracking catalyst increasing the weight of along with coking degree in operational process, in order to maintain transformation efficiency or diesel product quality, service temperature must be improved, and along with the raising of this temperature, the selectivity of cracking process must decline, diesel product yield can decline, if now the second hydrocarbon fraction is through the second hydrogenation process, the diesel yield based on the second hydrocarbon fraction can significantly decline, and the present invention then avoids this problem.

Embodiment two

Compared with embodiment one, second hydrogenation reaction effluent is incorporated into the special thermal high separate part AHPS of the second hydrogenation reaction effluent by the present embodiment, it is 280 ~ 310 DEG C in temperature, pressure is be separated into hot high score gas and hot high score oil under the condition of 11.0 ~ 13.0MPa, cycling hot high score oil RHPO is the hot high score oil of 33 ~ 66%, RHPO is recycled to the first hydrogenation reaction part or is recycled directly to the second hydrogenation reaction part, specific aim can improve the first hydrogenation reaction part material oil nature, form the oil circulation hydrocracking flow process of hot high score simultaneously, suitably can reduce the second hydrogenation reaction part oil product cracking per pass, reduce gas yield.

One of concrete scheme is that cycling hot high score oil is separated into cycling hot low point of gas and cycling hot low point of oil after step-down, and cycling hot low point of oil enters the first hydrogenation reaction part after pump (this pump and the first hydrocarbon fraction force (forcing) pump public) pressurizes; Two of concrete scheme is that the source line that the oily RHPO of cycling hot high score directly enters the second hydrogenation reaction partial hydrogenation reactor after force (forcing) pump mixes with the first hydrogenation reaction effluent.

Compared with embodiment 1, the to be cracked oily V recycle stream that high score oil separation section returns the second hydrogenation reaction part can be cancelled, form short route circulation loop, scale and the investment of high score oil separation section can be reduced, reduce power loss.

This programme is suitable for the low situation of the second hydrogenation reaction part per pass conversion, can simple flow, reduction energy consumption.

Embodiment three

Compared with embodiment one, the present embodiment adopts Hydrogenation raw oil once namely not use any recycle stream by flow process, but the second hydrogenation reaction part per pass conversion is improved, method be hydrocracking catalyst loadings add one times namely air speed reduce one times, high score oil separation section hydrogenated products quality is suitable, but gas yield adds 1.2 ~ 1.5% (relative to hydrogenating materials weight of oils), naphtha yield adds 4.7 ~ 6.0% (relative to hydrogenating materials weight of oils), diesel yield decline 5.9 ~ 7.5% (relative to hydrogenating materials weight of oils).

This programme is suitable for small-scale device, can simple flow, reduction energy consumption.

Embodiment four

Character is as the liquefaction oil of certain brown coal medium-pressure hydrocracking direct liquefaction process of table 1 oil product D, and its hydroconversion process adopts the present invention, and its major objective produces fine-quality diesel oil cut, and the step of employing, hydrogenation catalyst, product quality indicator are with embodiment one.Compared with embodiment one; in second hydrogenation reaction effluent, diesel oil distillate character is close; because liquefaction oil quality is inferior to modified oil, so all corresponding increase of the first hydrogenation reaction partial hydrogenation catalyzer (comprising Hydrodemetalation catalyst, hydrogenation protecting agent, hydrofining agent) quantity.Compared with embodiment one; in 3rd hydrogenation reaction effluent, diesel oil distillate character is close; because liquefaction oil quality is inferior to modified oil, so all corresponding increase of the 3rd hydrogenation reaction partial hydrogenation catalyzer (comprising Hydrodemetalation catalyst, hydrogenation protecting agent, hydrofining agent) quantity.

Although only enumerate four embodiments herein, be enough to show effect of the present invention.

Claims

1. different boiling ranges height aromatic hydrocarbons high-density hydrocarbon oil hydrogenation transforms a combined method, comprises the steps:

2. method according to claim 1, is characterized in that:

3. method according to claim 2, is characterized in that:

First hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

3rd hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

4. method according to claim 1, is characterized in that:

5. method according to claim 2, is characterized in that:

2. in the 4th hydrogenation reaction part, 3rd hydrogenation reaction effluent complete double ring arene open loop rate higher than 40% highly selective double ring arene hydrogenation ring-opening reaction be converted into the 4th hydrogenation reaction effluent, the 4th hydrogenation conditions is: temperature is 250 ~ 420 DEG C, pressure is 7.0 ~ 24.0MPa, the 4th hydrogenation catalyst possesses highly selective double ring arene hydrogenation open loop function, the 4th hydrogenation catalyst volume space velocity is 0.25 ~ 2.0hr-1, hydrogen/stock oil volume ratio is 500: 1 ~ 2000: 1.

6. method according to claim 5, is characterized in that:

First hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

3rd hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

4th hydrogenation conditions is: pressure is 10.0 ~ 20.0MPa;

7. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

3. the first hydrocarbon fraction hydrogenating reaction effluent and the second hydrocarbon fraction hydrogenating reaction effluent enter high pressure separate part through heat exchange temperature-fall period after directly mixing.

8. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

5. in high score oil separation section, obtain one primarily of the to be cracked oily V of 20 DEG C of density higher than the hydrocarbon component composition of 900 kilograms/cubic metre, oily V to be cracked goes the second hydrogenation reaction part to contact with the second hydrogenation catalyst at least partially.

9. method according to claim 4, is characterized in that:

10. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

5. in high score oil separation section, obtain one primarily of the to be cracked oily V of 20 DEG C of density higher than the hydrocarbon component composition of 900 kilograms/cubic metre, oily V to be cracked goes the first hydrogenation reaction part to contact with the first hydrogenation catalyst at least partially.

11. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

5. in high score oil separation section, obtain one primarily of normal boiling point be 120 ~ 170 DEG C hydrocarbon component composition petroleum naphtha PAC, part petroleum naphtha PAC goes the 3rd hydrogenation reaction part to contact with the 3rd hydrogenation catalyst.

12. methods according to claim 4 or 5 or 6, is characterized in that:

5. in high score oil separation section, obtain one primarily of normal boiling point be 165 ~ 265 DEG C hydrocarbon component composition solar oil HD1, part solar oil HD1 goes the 4th hydrogenation reaction part to contact with the 4th hydrogenation catalyst.

13. methods according to claim 9, is characterized in that:

1. the first hydrocarbon fraction nitrogen content is lower than 800PPm, and 20 DEG C of density are higher than 960 kilograms/cubic metre;

First hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

Second hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

In first hydrocarbon fraction hydrogenating reaction effluent, the nitrogen content of petroleum naphtha component is lower than 2PPm, and the cetane value of diesel component is higher than 30;

2. the second hydrocarbon fraction nitrogen content is lower than 300PPm, and 20 DEG C of density are higher than 930 kilograms/cubic metre;

3rd hydrogenation conditions is: pressure is 10.0 ~ 15.0MPa;

4th hydrogenation conditions is: pressure is pressure is 10.0 ~ 15.0MPa;

14. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

15. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

16. methods according to claim 15, is characterized in that:

1. the second hydrogenation reaction effluent enters thermal high separate part AHPS, temperature be 250 ~ 350 DEG C, pressure is separated into hot high score gas and hot high score oil under being the condition of 10.0 ~ 20.0MPa, hot high score oil returns the second hydrogenation reaction part and contact with the second hydrogenation catalyst as the oily RHPO of cycling hot high score at least partially.

17. methods according to claim 16, is characterized in that:

1. cycling hot high score oil RHPO weight rate is 15 ~ 150% of the first hydrocarbon fraction weight rate.

18. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:

19. methods according to claim 7, is characterized in that:

20. methods according to claim 8, is characterized in that: