CN104593060B - A kind of method of coal tar boiling bed hydrogenation - Google Patents

Abstract

A kind of method that the invention discloses coal tar boiling bed hydrogenation.The method is by after coal tar raw material first hydrogenated modification, is separated off water, more hydrogenated refined, is fractionated into obtaining gasoline fraction, diesel oil distillate and hydrogenation tail oil.The catalyst for hydro-upgrading composition wherein used includes that hydroxyl ferrum oxide, organic polycarboxylic acid, macroporous aluminium oxide, molecular sieve and boehmite, Hydrobon catalyst composition include FeOOH, organic polycarboxylic acid, macroporous aluminium oxide and binding agent.The present invention uses cheap FeOOH to use as catalyst for hydro-upgrading and the Hydrobon catalyst grating of active metal component, low cost, and can realize coal tar first appropriateness cracking is refined again, the effectively impurity in removing coal tar, adjust product slates and product property, and the service cycle of energy extension fixture.

Description

A kind of method of coal tar boiling bed hydrogenation

Technical field

A kind of method that the present invention relates to coal tar hydrogenating, is particularly well-suited to the boiling bed hydrogenation cracking process of coal tar.

Background technology

Coal tar is an important side-product during pyrolysis of coal distillation process, is the complex mixture of many kinds of substance, According to pyrolysis of coal pyrolysis temperature and the difference of process approach, coal tar can be divided into coalite tar and high temperature coal-tar.

Compared with oil heavy distillat, it is high that coal tar raw material has the content of heteroatoms such as sulfur, nitrogen, and ash is high, and polycyclic aromatic hydrocarbon contains Amount is high, resin and asphalt content high.Therefore directly burning can produce substantial amounts of sulfide and nitride, causes serious Environmental pollution.Coal tar clean processing and effectively utilization become more important.Hydrogenation technique is utilized can effectively to remove coal The impurity such as sulfur in tar, nitrogen, reduce its density, it is achieved lighting.

Coal tar hydrogenating processes and mainly includes that hydrofinishing and hydro-upgrading, hydrofinishing main purpose are to remove coal The hetero atoms such as sulfur in tar, nitrogen, oxygen, improve product quality；The main purpose of hydro-upgrading is to change coal tar further The molecular structure of each component in oil, as saturated in aromatic hydrogenation, polycyclic aromatic hydrocarbon open loop etc..Compared with distillate hydrogenation, coal tar adds Hydrogen modifying catalyst faces the challenge in terms of following four: one is that oxygen content is high, and the water that deoxidation produces is to the activity of catalyst, steady Qualitative and intensity all produces very adverse influence, and two is that colloid, carbon residue content height easily promote catalyst carbon deposit, causes catalysis Agent inactivation and bed blocking, three is sulfur, nitrogen content height, it is desirable to deep hydrogenation denitrogenation, otherwise stability does not reaches requirement, and four is coal Containing substantial amounts of aromatic hydrocarbons in tar, in its diesel oil distillate, Cetane number is the lowest, it is desirable to deeply hydrodearomatized, and is reducing as far as possible On the premise of chain rupture, aromatic hydrocarbons is saturated to greatest extent and open loop, makes every effort to improve to greatest extent diesel cetane-number.

CN201010228569.5 discloses a kind of coal tar hydrogenating and generates group technology and the catalysis thereof of clean fuel oil Agent.The method is to use fixed bed group technology, and catalyst for hydro-upgrading active component therein is group VIII and vib Metal-oxide NiO, MoO₃、CoO、WO₃One or more, carrier is the Kaolin that acid is modified.Owing to using the modified kaolinite of acid Soil is as carrier, and its pore volume is the least and acidity is higher, therefore for the coal tar raw material that colloid and asphalt content are higher, colloid Enter less than in catalyst duct with asphalitine, form more carbon deposit at catalyst surface, so that catalyst easily inactivates, fortune The turn-week phase is short.

CN200910010781.1 discloses a kind of catalyst for coal tar hydrogenation modification and preparation method thereof.The method is lived Property metal is WO₃, NiO, and containing P₂O₅, wherein WO₃Content is 27% ~ 30%, NiO content 4% ~ 7%, P₂O₅Content 2% ~ 3%, carrier It is made up of aluminium oxide and ZSM-5 molecular sieve.CN200510048573.2 disclose a kind of catalyst for coal tar hydrogenation modification and Preparation method.This catalyst WO₃、MoO₃Mixture or WO with NiO₃With the mixture of NiO, account for the 29% of total catalyst weight ~ 35%, carrier is made up of silicon oxide, aluminium oxide and Y molecular sieve.

The conventionally used active metal component of coal tar hydrogenation catalyst is W, Mo, Ni, Co etc., and it is expensive, and adopts Substitute with cheap active metal and reduce the emphasis that catalyst cost is research.

FeOOH (FeOOH) is widely present in mine, waste water, soil and water sediment as a kind of nonmetallic mineral Deng in natural environment, generally exist with multiple solid tetraploid forms such as goethitum, lepidocrocite and akaganeites.Hydroxyl oxidize Ferrum is very important material in industrial application, as can serve as the presoma of fuel, catalyst, magnetic recording media, Functional material it is also used as, such as gas sweetening agent, the scavenger of heavy metal in waste water during environmental conservation.

In CN201010272981.7 and CN200710001215.5 all be use coal dust be carrier, with molybdenum, nickel, tungsten or cobalt The molecular level high-activity component of one or more mixture of water soluble salt compounds and/or nano level low activity component R-FeOOH particle prepares catalyst.Catalyst grain size is 1-100 micron, it is adaptable to coal tar hydrogenating process.In this patent Catalyst grain size is the least, it is adaptable to floating bed hydrogenation process, is not suitable for boiling bed hydrogenation.

CN201310107002.6 discloses a kind of Organic sulphur hydrogenation catalyst, and it includes the Al of specified weight part₂O₃Carry Body, ZnO, iron oxides and molybdenum oxide, its preparation method is that ferric nitrate and ammonium molybdate are made active component solution, then exists Al₂O₃In carrier preparation process, add active component solution, after drying, add the zinc oxide of 36 ~ 44 weight portions, and without fixed Shape FeOOH, i.e. obtains described Organic sulphur hydrogenation catalyst after molding, roasting.This catalyst adds in preparation process Amorphous FeOOH, but be converted into ferrum oxide after final high-temperature roasting, therefore, the final performance of gained catalyst Depend on ferrum oxide, rather than FeOOH.

Full fraction of coal tar is first passed through flash distillation by CN02122573.7 remove less than C₅After lighter hydrocarbons, 4 switchings protecting Protect reactor and carry out pre-hydrofinishing, subsequently into boiling bed hydrogenation reactor, at MoO₃-WO₃-Ni-P-TiO₂Catalyst action Under, hydrogenation reactor inlet pressure is not more than 15.0MPa(hydrogen dividing potential drop), initial reaction temperature is 300 ~ 390 DEG C, volume space velocity 0.4~4.0h^-1, hydrogen-oil ratio 500 ~ 3000Nm³/m³.Coal tar raw material is carried out by the method really switching fixed-bed process process Hydrofinishing, but due to impurity content height in coal tar, and react easy coking under the high temperature conditions, cause beds to hinder Plug phenomenon is serious, and long-term operation to be kept needs the most more catalyst changeout, and catalyst amount is big, adds cost, and technique is multiple Miscellaneous.In addition switching reactor product out contains considerable amount of water, unprocessed is directly entered hydrogenation reactor, to catalyst (especially with the catalyst of molecular sieve) activity influence is very big, and catalyst activity can be caused to be substantially reduced.

Summary of the invention

For deficiency of the prior art, a kind of method that the invention provides coal tar boiling bed hydrogenation.Side of the present invention Coal tar first appropriateness cracking can be refined by method again, and effectively the impurity in removing coal tar, adjusts product slates and product Character, and the service cycle of energy extension fixture.

The method of coal tar boiling bed hydrogenation of the present invention, including:

A, coal tar raw material and hydrogen are mixed into the first boiling bed hydrogenation reactor carry out hydro-upgrading, hydrotreating After generation oil enter oily-water seperating equipment, be separated off water；

B, except after water hydrotreating generate oil enter the second boiling bed hydrogenation reactor carry out hydrofinishing, hydrofinishing After product enter fractionating system, obtain gasoline fraction, diesel oil distillate and hydrogenation tail oil after fractional distillation.

In the inventive method, step A coal tar raw material is before entering hydrogenation reactor, preferably through pretreatment, typically Preprocess method is dehydration and removes mechanical admixture.Dehydration makes water content in raw material be less than 0.5wt%.

Step A coal tar hydrogenating feed needs ash is not more than 0.015%, and water content is less than 0.5wt%.

Step A and B relate to fluidized bed reactor and can use conventional fluidized bed reactor of the prior art.Ebullated bed Hydroprocessing condition can require specifically to determine according to feedstock property and product, generally: reaction temperature is 330～420 DEG C, Best 350～420 DEG C；Reaction pressure is 8～25MPa, preferably 8.0～16MPa；Hydrogen to oil volume ratio 300:1 ~ 1000:1, It is well 500:1 ~ 1000:1；Liquid volume air speed (LHSV) is 0.3～5.0h^-1, preferably 0.3～2.0h^-1。

In step A, catalyst for hydro-upgrading used in the first boiling bed hydrogenation reactor, it is designated as an anti-hydrogenation catalyst Agent, specific as follows:

One anti-hydrogenation catalyst includes FeOOH, macroporous aluminium oxide, molecular sieve, organic polycarboxylic acid and plan thin water aluminum Stone, on the basis of the weight of catalyst, its composition is as follows: the content of FeOOH is 10wt% ~ 50wt%, preferably 20wt% ~ 50wt%, the content of macroporous aluminium oxide is 20wt% ~ 60wt%, preferably 35wt% ~ 60wt%, the content of molecular sieve be 3wt% ~ 15wt%, preferably 5wt % ~ 15wt %, the content of boehmite is 5 wt % ~ 40 wt %, preferably 10 wt % ~ 30 wt %；Wherein the content of organic polycarboxylic acid is 0.05 ~ 0.40g/g FeOOH, preferably 0.10 ~ 0.35g/g hydroxyl oxidize Ferrum.

The anti-hydrogenation catalyst of the present invention one, the character of described macroporous aluminium oxide is as follows: specific surface area 160 ~ 250m²/ g, Pore volume 0.80 ~ 1.20mL/g, average pore diameter is 13 ~ 25nm.Described macroporous aluminium oxide can also add conven-tional adjuvants group Point, such as one or more of P, B, Si, F etc., in terms of element, adjuvant component weight content in the catalyst is 0 ~ 5.0%, excellent Elect 0.1% ~ 5.0% as.

In the anti-hydrogenation catalyst of the present invention one, described molecular sieve preferably employs Y type molecular sieve and/or beta-molecular sieve.Above-mentioned Molecular sieve all uses hydrogen type molecular sieve.Described Y type molecular sieve character is as follows: SiO₂/Al₂O₃Mol ratio is 10 ~ 15；Described beta molecule Sieve character is as follows: SiO₂/Al₂O₃Mol ratio is 40 ~ 80.

In the present invention one anti-hydrogenation catalyst, described organic polycarboxylic acid is in citric acid, malic acid, tartaric acid One or more.

The character of the anti-hydrogenation catalyst of the present invention one is as follows: pore volume is 0.50 ~ 1.00mL/g, and specific surface area is 150 ~ 300m²/ g, preferably 150 ~ 250m²/ g, pore size distribution is as follows: the bore dia pore volume in the hole of 10nm ~ 50nm account for total pore volume 10% ~ 50%, preferably 25% ~ 40%.Catalyst granules is microspheroidal, a diameter of 0.1～0.8mm, preferably 0.3～0.8mm；Rate of wear≤ 2.0wt%。

The character of the anti-hydrogenation catalyst of the present invention one is as follows: pore volume 0.40 ~ 0.90mL/g, and specific surface area is 150 ~ 250m²/ G, pore size distribution is as follows: the bore dia pore volume in the hole of 10nm ~ 50nm accounts for the 20% ~ 40% of total pore volume.

The preparation method of the anti-hydrogenation catalyst of the present invention one, including:

(1) in FeOOH filter cake, add organic polycarboxylic acid, mix homogeneously, after being then passed through filter, obtain modified filter Cake；

(2) prepare alumine hydroxide colloid, alumine hydroxide colloid prepare before, among or afterwards add macroporous aluminium oxide and Molecular sieve, obtains the alumine hydroxide colloid containing macroporous aluminium oxide and molecular sieve；

(3) colloid of step (2) gained being regulated pH value is 6.5 ~ 7.5, preferably 6.5 ~ 7.0, add step (1) gained Serosity, then carries out aging, filters, and washing is dried so that it is solid content is 30wt% ~ 40wt%；

(4) material of step (3) gained is shaped, through obtaining hydrogenation catalyst after drying.

FeOOH filter cake used in the inventive method uses wet method oxygen-containing gas oxidizing process to prepare.General mistake After Cheng Shi: ferrous salt and alkali reaction generate ferrous hydroxide precipitation, then obtain the mixed of hydroxyl ferrum oxide through oxygen-containing gas oxidation Compound, obtains FeOOH filter cake through filtering, washing.The concrete preparation process of FeOOH filter cake is as follows: by ferrous salt (such as ferrous sulfate) aqueous solution and alkaline solution (such as sodium hydroxide solution) mix, and obtain containing ferrous hydroxide Suspension；Control suspension, at-5 DEG C ~ 10 DEG C, in suspension, to be blown into oxygen-containing gas (such as air), obtain hydroxyl oxidize The precursor of iron particle；Control temperature, at 20 DEG C ~ 45 DEG C, is blown into oxygen-containing gas (such as in iron oxyhydroxide particle precursor Air), thus generate iron oxyhydroxide particle, obtain FeOOH filter cake through filtering, washing above-mentioned serosity.

The organic polycarboxylic acid in mixed process described in step (1) is citric acid, malic acid, tartaric one or several Kind, the process time is 0.5 ~ 3.0h, the method for grinding can be used to be conducive to quick mix homogeneously, and reduce FeOOH Particle diameter, the granularity of FeOOH preferably below 30 microns, further preferred less than 20 microns, much further preferably from 5 ~ 20 Micron, in serosity, solids content is less than 60wt%, preferably smaller than 45wt %.

The character of the macroporous aluminium oxide in step (2) is as follows: specific surface area 160 ~ 250m²/ g, pore volume 0.80 ~ 1.20mL/ G, average pore diameter is 13 ~ 25nm.Described macroporous aluminium oxide can also add conven-tional adjuvants component, such as P, B, Si, F etc. One or more, in terms of element, adjuvant component weight content in the catalyst is 0 ~ 5%, preferably 0.1% ~ 5%.Macropore oxygen Change aluminum be use boehmite or containing the boehmite of auxiliary agent fired after obtain, roasting condition is as follows: roasting temperature Degree is 500 ~ 900 DEG C, preferably 600 ~ 900 DEG C, and roasting time is 1 ~ 24h, preferably 2 ~ 8h.

In the anti-hydrogenation catalyst of the present invention one, described molecular sieve preferably employs Y type molecular sieve and/or beta-molecular sieve.Above-mentioned Molecular sieve all uses hydrogen type molecular sieve.Described Y type molecular sieve character is as follows: SiO₂/Al₂O₃Mol ratio is 10 ~ 15；Described beta molecule Sieve character is as follows: SiO₂/Al₂O₃Mol ratio is 40 ~ 80.

Step (2) is prepared alumine hydroxide colloid and the method for routine can be used to carry out, and conventional method is acid-base neutralization plastic Method, i.e. uses aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to be neutralized the process of reaction, wherein used solvable Property aluminium salt is one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, and acidic precipitation agent used is usually hydrochloric acid, sulphuric acid, nitre One or several in acid, oxalic acid, carbon dioxide etc., alkaline precipitating agent used is usually sodium carbonate, sodium bicarbonate, hydrogen-oxygen Change in sodium, potassium hydroxide, ammonia etc. one or several.Aluminium oxide plastic can also use meta-aluminate (such as meta-aluminic acid Sodium and/or potassium metaaluminate) it is neutralized into acid aluminium salt (one or more in such as aluminum chloride, aluminum nitrate, aluminum sulfate) The method of glue.The present invention prepares alumine hydroxide colloid and can use and flow plastic, it would however also be possible to employ acid addition or alkali addition plastic.Institute The plastic process stated typically is carried out at room temperature ~ 85 DEG C, is relatively suitably for 40 ~ 80 DEG C, preferably 50 ~ 80 DEG C.Described plastic mistake Journey is typically carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, relatively it is suitably for 7.0 ~ 9.5, preferably 7.5 ~ 9.0.Macroporous aluminium oxide can alumine hydroxide colloid prepare before, among or add afterwards, specific as follows: (1) by macropore aoxidize Aluminum and molecular sieve are added in bottom water or raw material add；(2) in aluminium hydroxide and during plastic, by macroporous aluminium oxide and molecule Sieve once or several times or is continuously added to；(3) macroporous aluminium oxide and molecular sieve are added after aluminium hydroxide plastic.

Aging condition described in step (3) is as follows: aging temperature 120 DEG C ~ 250 DEG C, preferably 150 DEG C ~ 220 DEG C, time aging Between be 1 ~ 24h, preferably 2 ~ 10h.Dry described in step (3) is to carry out at 50 ~ 90 DEG C so that it is containing solid content be 30wt% ~ 40wt%。

Wherein step (4) is shaped to microspheroidal.Baking temperature described in step (4) is 50 ~ 200 DEG C, preferably 90 ~ 180 ℃。

In the inventive method, Hydrobon catalyst used in the second boiling bed hydrogenation reactor, it is designated as two and counter is hydrogenated with Catalyst, this catalyst includes FeOOH, macroporous aluminium oxide, organic polycarboxylic acid and adhesive component, with catalyst On the basis of weight, its composition is as follows: the content of FeOOH is 20wt% ~ 70wt%, preferably 30wt% ~ 60wt%, macropore oxygen The content changing aluminum is 10wt% ~ 50wt%, preferably 20wt% ~ 50wt%, and the content of binding agent is 1% ~ 20%, preferably 3% ~ 15%； Wherein the content of organic polycarboxylic acid is 0.05 ~ 0.40g/g FeOOH, preferably 0.10 ~ 0.35g/g FeOOH.

The character of the anti-hydrogenation catalyst of the present invention two is as follows: specific surface area is 150～300m²/ g, pore volume is 0.35 ~ 0.70mL/g, bore dia at least accounts for the 60% of total pore volume at the pore volume shared by the hole of 5～15nm, and catalyst granules is microspheroidal, directly Footpath is 0.1～0.8mm, preferably 0.3～0.8mm；Rate of wear≤2.0wt%.

The preparation method of the anti-hydrogenation catalyst of the present invention two, including:

(1) in FeOOH filter cake, add organic polycarboxylic acid, mix homogeneously, after being then passed through filter, obtain modified filter Cake；

(2) it is shaped after the modified filter cake prepared by step (1) and macroporous aluminium oxide, binding agent mix homogeneously, passes through Obtain two anti-hydrogenation catalysts after drying.

The present invention two anti-hydrogenation catalyst same anti-hydrogenation catalyst of step (1) preparation process.Macropore oxygen in step (2) The character changing aluminum is as follows: specific surface area 160 ~ 250m²/ g, pore volume 0.80 ~ 1.20mL/g, average pore diameter is 13 ~ 25nm.Described Macroporous aluminium oxide in can also add conven-tional adjuvants component, such as one or more of P, B, Si, F etc., auxiliary agent in terms of element Component weight content in the catalyst is 0 ~ 5%, preferably 0.1% ~ 5%.Macroporous aluminium oxide is to use boehmite or contain Obtaining after the boehmite of auxiliary agent is fired, roasting condition is as follows: sintering temperature is 500 ~ 900 DEG C, and preferably 600 ~ 900 DEG C, roasting time is 1 ~ 24h, preferably 2 ~ 8h.One anti-hydrogenation catalyst and two anti-hydrogenation catalysts can use identical macropore Aluminium oxide, it would however also be possible to employ different macroporous aluminium oxides.

In the anti-hydrogenation catalyst of the present invention two, binding agent can use the binding agent of routine, preferably Polyethylene Glycol, polyethylene One or more of alcohol, POLYPROPYLENE GLYCOL, polypropylene amine, methylcellulose etc..

In step B, hydrogenation tail oil can partly or entirely circulate, and its addition is the second fluidized bed reactor Raw material processing Below the 40wt% of amount, generally 5wt% ~ 40wt%, preferably 10wt% ~ 30wt%.

The invention have the advantages that

(1) boiling bed hydrogenation technique is used to process coal tar, active in ensureing reactor by online interpolation catalyst Unanimously, thus the impurity in the service cycle of extension fixture, the most more preferably removing coal tar, and the preferably saturated performance of aromatic hydrocarbons.

(2) in boiling bed hydrogenation reactor of the present invention, an anti-hydrogenation catalyst and two anti-hydrogenation catalysts all use price low Honest and clean FeOOH is as active metal component, and introduces a small amount of organic polycarboxylic acid, in FeOOH, macropore oxidation Build bridge between aluminum (or macroporous aluminium oxide and molecular sieve), promote FeOOH and macroporous aluminium oxide (or macroporous aluminium oxide And molecular sieve) form suitable interaction, make catalyst both be prone to sulfuration, the most beneficially FeOOH stable and equably It is distributed in the surface of macroporous aluminium oxide (or macroporous aluminium oxide and molecular sieve), makes an anti-hydrogenation catalyst have higher hydrogenation and live Property, suitable lytic activity and preferable stability, two anti-hydrogenation catalysts have higher hydrogenation activity and the most stable Property, thus when realizing using plural serial stage boiling bed hydrogenation technique, processing sequence refined after first cracking, so can be effectively Process coal tar, and improve product slates and product property.

(3) hydrogenation tail oil circulation joins in the first fluidized bed reactor, it is possible to coal tar raw material is played diluting effect, Make its character be improved, reduce boiling bed hydrogenation reaction difficulty and processing severity, oil property can be improved further, Reduce the hydrogen consumption of device.

Accompanying drawing explanation

Fig. 1 is coal tar hydrogenating group technology schematic flow sheet of the present invention.

Wherein, 1 raw material, 2 waste water, 3 raw oil water separation devices, 4 hydrogen, 5 first boiling bed hydrogenation reactors, 6 Intermediate products oily-water seperating equipment, 7 second boiling bed hydrogenation reactors, 8 distillation column, 9 tail gas, 10 gasoline, 11 diesel oil, 12 Hydrogenation tail oil, 13 water generation reactions；

Fig. 2 is the S content distribution figure in coal tar operating in hydrogenation tail oil.

Detailed description of the invention

The method provided the present invention below in conjunction with Fig. 1 further illustrates.

Coal tar raw material 1 first passes through raw oil water separation device 3, and the water content removing the coal tar raw material after waste water 2 is little In 0.5wt%, ash is not more than 0.015wt%.Then mix with hydrogenation tail oil 12 and hydrogen 4, enter the first boiling bed hydrogenation anti- Answer device 5, under an anti-hydrogenation catalyst and hydroconversion condition, carry out hydrocracking reaction, make coal tar appropriateness cracking removing portion simultaneously The hetero atoms such as parting genus, sulfur, make asphalitine, colloid convert.Product after being hydrocracked enters the oil-water separation dress of intermediate products Put 6 and be removed water generation reaction 13.Generation oil after process enters the second boiling bed hydrogenation reactor 7, is instead hydrogenated with two and urges Agent contacts, and carries out hydrogenation reaction under certain hydroconversion condition, and removing part further, except the hetero atom such as metal, sulfur, makes Colophonium Matter, colloid convert and aromatic hydrocarbons is saturated, and the product after hydrotreating enters fractionating column 8, and fractional distillation obtains gasoline fraction 10, diesel oil distillate 11 and hydrogenation tail oil 12.

For further illustrating main points of the present invention, use the flow process of Fig. 1, enumerate following example, but do not limit its scope.

In the present invention, specific surface area, pore volume, average pore diameter and pore size distribution are to use low temperature liquid nitrogen determination of adsorption method. The particle size distribution of catalyst uses sieve method to measure.Abrasion use MH-1 type fluid bed wear and tear gauge to measure.In the present invention, Wt% is mass fraction.

It is addressed further under the technical characteristic of the present invention below by embodiment, but is not limited to embodiment.

Embodiment 1

Prepared by catalyst

1, prepared by an anti-hydrogenation catalyst I-1

Weigh FeOOH filter cake 1000g prepared by wet method air oxidation process, wherein contain FeOOH 400g, to It adds the stirring of 1L water-soluble 130g citric acid makes its mix homogeneously, and modification time 0.5h, the serosity after process is stand-by.

Preparation sodium aluminate solution concentration is 50gAl₂O₃/ L amounts to 1L, be heated to 80 DEG C stand-by, aluminum sulfate solution concentration is 20gAl₂O₃/ L amounts to 2L, be heated to 80 DEG C stand-by.

In plastic cans, add 1.0L distilled water, be heated to 80 DEG C.Weigh 450g(macroporous aluminium oxide specific surface area 162m²/ G, pore volume 0.84mL/g, average pore size is 21nm) and 150gY type molecular sieve (SiO₂/Al₂O₃=12.0), join in plastic cans Stirring, and flow addition sodium aluminate solution and aluminum sulfate solution, gelling temperature is maintained at 80 DEG C, and pH value remains 8.0.Become Regulating slurry pH value after cementing bundle is 7.0, puts into anti-after being subsequently adding the FeOOH serosity of citric acid treatment, mix homogeneously Answer still is carried out aging, aging temperature 150 DEG C, ageing time is 6h, aging rear product through filtration, obtain iron content hydroxyl after washing The aluminium oxide filter cake of base ferrum oxide and molecular sieve.

Being dried at 80 DEG C by above-mentioned filter cake so that it is solid content is 36wt%, weigh 200g and become ball forming, after molding, sample exists Sieving after being dried 5h at 150 DEG C, taking out granularity is that the sample of 0.3-0.5mm is as catalyst I-1.

2, prepared by an anti-hydrogenation catalyst I-2

Other condition is with I-1 catalyst, and simply preparation sodium aluminate solution concentration is 60gAl₂O₃/ L amounts to 2L, aluminum sulfate Solution concentration is 20gAl₂O₃/ L amounts to 4L, and in plastic cans, bottom water is 3L, and addition macroporous aluminium oxide is 800g, prepares catalysis Agent I-2.

3, prepared by an anti-hydrogenation catalyst I-3

Other condition, with I-1 catalyst, simply changes Y molecular sieve as beta-molecular sieve (SiO into₂/Al₂O₃=60), prepare and urge Agent I-3.

4, prepared by two anti-hydrogenation catalyst II-1

Weigh FeOOH filter cake 1000g prepared by wet method air oxidation process, wherein contain FeOOH 400g, to It adds the stirring of 1000mL water-soluble 80g citric acid makes its mix homogeneously, modification time 1h, obtains after being then passed through filter Modified filter cake.

Weigh 170g modification filter cake (wherein hydroxyl ferrum oxide 60g, citric acid 16g) and 70g specific surface area respectively 230m²/ g, pore volume 0.91mL/g, average pore size is the macroporous aluminium oxide of 16nm, and becomes after 5g Polyethylene Glycol mix homogeneously Ball forming, after molding, sample sieves after being dried 4h at 150 DEG C, and taking out granularity is that the sample of 0.3-0.5mm is as catalysis Agent II-1.

5, prepared by two anti-hydrogenation catalyst II-2

Weigh FeOOH filter cake 1000g prepared by wet method air oxidation process, wherein contain FeOOH 400g, to It adds the stirring of 1000mL water-soluble 120g malic acid makes its mix homogeneously, modification time 1.5h, after being then passed through filter Obtain modified filter cake.

Weigh 160g modification filter cake (wherein hydroxyl ferrum oxide 51g, malic acid 15g) and 50g specific surface area respectively 200m²/ g, pore volume 0.90mL/g, average pore size is the macroporous aluminium oxide of 18nm, and 3g polyvinyl alcohol uniformly after become Ball forming, after molding, sample sieves after being dried 3h at 120 DEG C, and taking out granularity is that the sample of 0.3-0.5mm is as catalysis Agent II-2.

Comparative example 1

Weigh FeOOH filter cake 1000g prepared by wet method air oxidation process, wherein contain FeOOH 400g, to It adds 1L water and stirs, and the serosity obtained is stand-by.

Preparation sodium aluminate solution concentration is 50gAl₂O₃/ L amounts to 1L, be heated to 80 DEG C stand-by, aluminum sulfate solution concentration is 20gAl₂O₃/ L amounts to 2L, be heated to 80 DEG C stand-by.

In plastic cans, add 1.0L distilled water, be heated to 80 DEG C.Weigh 580g(macroporous aluminium oxide specific surface area 162m²/ G, pore volume 0.84mL/g, average pore size is 21nm) and 150gY type molecular sieve (SiO₂/Al₂O₃=12.0), join in plastic cans Stirring, and flow addition sodium aluminate solution and aluminum sulfate solution, gelling temperature is maintained at 80 DEG C, and pH value remains 8.0.Become Regulating slurry pH value after cementing bundle is 7.0, puts into and carry out in reactor always after being subsequently adding FeOOH serosity, mix homogeneously Changing, aging temperature 150 DEG C, ageing time is 6h, and aging rear product, through filtering, obtains iron content FeOOH and divides after washing The aluminium oxide filter cake of son sieve.

Being dried at 80 DEG C by above-mentioned filter cake so that it is solid content is 36wt%, weigh 200g and become ball forming, after molding, sample exists Sieving after being dried 5h at 150 DEG C, taking out granularity is that the sample of 0.3-0.5mm is as catalyst F-1.

Comparative example 2

Weigh amorphous FeOOH 40g, boehmite 22g, 15gY type molecular sieve and 45g macroporous aluminium oxide (big Porous aluminum oxide specific surface area 162m²/ g, pore volume 0.84mL/g, average pore size is 21nm) and 65g water mix homogeneously after, balling-up becomes Type, after molding, sample sieves after being dried 5h at 150 DEG C, and taking out granularity is that the sample of 0.3-0.5mm is as catalyst F- 2。

Catalyst physico-chemical property obtained by above is listed in table 1.

The physico-chemical property of table 1 catalyst

Table 1 continues

Embodiment 2

Catalyst I-1, I-2, I-3 and II-1, II-2 on the continuous stirring autoclave of series connection (CSTR) are carried out activity Evaluating, the filling of each reactor catalyst is 100mL, and evaluating coalite tar in selecting is raw oil, and its character is shown in Table 2, work Skill condition is shown in Table 3, and evaluation result is shown in Table 4, table 5 and table 6.

Table 2 raw oil character

Process conditions evaluated by table 3

Table 3 continues

Table 4 gasoline fraction character (C₅-180 DEG C)

Analysis project	T-1	T-2	T-3	T-4	T-5	T-6	T-7
								Yield, wt%	21.6	22	22.8	23.3	23.1	22.6	22.2
Density (20 DEG C), kg/m3	0.7535	0.7524	0.7520	0.7501	0.7511	0.7509	0.7528
								Sulfur, g/g	11	9.7	8.9	7.2	7.7	8.1	9
Research octane number (RON) RON	84.8	85.9	86.7	88.3	87.2	87.9	86.9
								Boiling range, DEG C
Initial boiling point	97	94	90	83	85	85	94
								50%	160	155	152	146	151	150	159
The end point of distillation	189	184	180	176	178	179	187

Table 5 diesel oil distillate character (180-350 DEG C)

Analysis project	T-1	T-2	T-3	T-4	T-5	T-6	T-7
								Yield, wt%	68.2	68.5	68.8	69.2	69	69	68.6
Density (20 DEG C), kg/m3	0.8647	0.8613	0.8609	0.8588	0.8592	0.8603	0.8610
								Sulfur, g/g	25	24	22	20	21	21	23
Condensation point, DEG C	-10	-12	-13	-15	-15	-14	-13
								Cetane number	40.6	42.1	42.9	43.4	43.3	43.0	42.6
Boiling range, DEG C
								10%	185	183	181	178	179	180	182
50%	300	297	293	292	292	293	295
								95%	367	363	359	353	353	357	362

350 DEG C of table 6 hydrogenation tail oil character (>)

Project	T-1	T-2	T-3	T-4
					Yield, wt%	7.6	5.8	4.6	3.9
Density (20 DEG C), kg/m3	0.9292	0.9289	0.9283	0.9270
					Sulfur, g/g	111	104	103	98
Carbon residue, wt%	1.08	1.01	0.98	0.90
					Boiling range, DEG C
Initial boiling point	355	353	353	351
					50%	435	432	431	428
The end point of distillation	533	531	529	526

Table 6 continues

Project	T-5	T-6	T-7
				Yield, wt%	4.1	4.3	5.9
Density (20 DEG C), kg/m3	0.9278	0.9281	0.9285
				Sulfur, g/g	101	100	104
Carbon residue, wt%	0.92	0.94	0.99
				Boiling range, DEG C
Initial boiling point	352	352	353
				50%	428	430	431
The end point of distillation	528	528	530

Knowable to above evaluation result: coal tar after the technique of the present invention and catalyst hydrogenation process, the vapour of generation Oil, diesel oil all can be as the blend components of high-quality, and hydrogenation tail oil character can be hydrocracked further and generate other products.

Embodiment 3

Selecting catalyst I-1/II-1 connects, and is 370 DEG C, reaction pressure 15MPa and air speed 0.5h in reaction temperature^-1Bar Normal operation 1000h under part, at different time respectively to the S sample analysis in hydrogenation tail oil, obtains catalyst at different time Hydrogenation activity see Fig. 2.

Comparative example 3

Catalyst F-1/II-1 connects, and is 370 DEG C, reaction pressure 15MPa and air speed 0.5h in reaction temperature^-1Under conditions of Normal operation 1000h, at different time respectively to the S sample analysis in hydrogenation tail oil, obtains catalyst adding at different time Hydrogen activity is shown in Fig. 2.

Comparative example 4

Catalyst F-2/II-1 connects, and is 370 DEG C, reaction pressure 15MPa and air speed 0.5h in reaction temperature^-1Under conditions of Normal operation 1000h, at different time respectively to the S sample analysis in hydrogenation tail oil, obtains catalyst adding at different time Hydrogen activity is shown in Fig. 2.

Comparative example 5

The catalyst provided in CN02122573.7 is provided, prepares coal tar hydrorefining catalyst (MF-1) and coal Hydrogenation of tar modifying catalyst (MF-2), its physico-chemical property is shown in Table 7.By above two catalyst MF-1/MF-2 in the company connected In continuous agitated autoclave, (CSTR) carries out activity rating, and the filling of each reactor catalyst is 100mL, is 370 in reaction temperature DEG C, reaction pressure 15MPa and air speed 0.5h^-1Under conditions of normal operation 1000h, at different time respectively in hydrogenation tail oil S sample analysis, obtains catalyst and sees Fig. 2 at the hydrogenation activity of different time.

The physico-chemical property of catalyst in table 7 comparative example

Numbering	MF-1	MF-2
			Catalyst forms
MoO3, wt%	15.02	15.36
			WO3, wt%	-	18.34
NiO, wt%	3.89	4.06
			P, wt%	0.98	1.26
TiO2, wt%	15.38	10.38
			Molecular sieve, wt%	-	7.98
Al2O3, wt%	Surplus	Surplus
			Catalyst property
Specific surface area, m2/g	198	220
			Pore volume, mL/g	0.472	0.401
Crushing strength, N/cm	≮15	≮15
			Outward appearance	Spherical	Spherical
Bulk density, g/mL	0.71	0.85

As can be seen from Figure 2: compared with comparative example, use catalyst and the technique of the present invention, generate oil nature and have good Good stability.

Claims (19)

1. a coal tar hydrogenating process, including:

A, coal tar raw material and hydrogen are mixed into the first boiling bed hydrogenation reactor carry out hydro-upgrading, after hydro-upgrading Generate oil and enter oily-water seperating equipment, be separated off water；

B, except after water hydrotreating generate oil enter the second boiling bed hydrogenation reactor carry out hydrofinishing, after hydrofinishing Product enters fractionating system, obtains gasoline fraction, diesel oil distillate and hydrogenation tail oil after fractional distillation；

Wherein, the anti-hydrogenation catalyst of catalyst for hydro-upgrading that is one that the first boiling bed hydrogenation reactor uses, composition includes hydroxyl Base ferrum oxide, organic polycarboxylic acid, macroporous aluminium oxide, molecular sieve and boehmite, on the basis of the weight of catalyst, its group Becoming as follows: the content of FeOOH is 10wt%～50wt%, the content of macroporous aluminium oxide is 20wt%～60wt%, molecular sieve Content is 3wt%～15wt%, and the content of boehmite is 5wt%～40wt%, and wherein the content of organic polycarboxylic acid is 0.05 ～0.40g/g FeOOH；

The anti-hydrogenation catalyst of Hydrobon catalyst that is two used in second boiling bed hydrogenation reactor, this catalyst includes hydroxyl Base ferrum oxide, macroporous aluminium oxide, organic polycarboxylic acid and adhesive component, on the basis of the weight of catalyst, its composition is as follows: The content of FeOOH is 20wt%～70wt%, and the content of macroporous aluminium oxide is 10wt%～50wt%, and the content of binding agent is 1 Wt%～20wt %；Wherein the content of organic polycarboxylic acid is 0.05～0.40g/g FeOOH.

The most in accordance with the method for claim 1, it is characterised in that step A coal tar raw material is entering before hydrogenation reactor, Through pretreatment, including dehydration with except mechanical admixture, making water content in raw material be less than 0.5wt%, ash is not more than 0.015%.

The most in accordance with the method for claim 1, it is characterised in that the hydroconversion condition that step A and B use is: reaction temperature is 330～420 DEG C；Reaction pressure is 8～25MPa；Hydrogen to oil volume ratio 300:1～1000:1；Liquid volume air speed be 0.3～ 5.0h^-1。

The most in accordance with the method for claim 1, it is characterised in that the hydroconversion condition that step A and B use is: reaction temperature is 350～420 DEG C；Reaction pressure is 8.0～16MPa；Hydrogen to oil volume ratio is 500:1～1000:1；Liquid volume air speed 0.3～ 2.0h^-1。

The most in accordance with the method for claim 1, it is characterised in that a described anti-hydrogenation catalyst, with the weight of catalyst it is Benchmark, its composition is as follows: the content of FeOOH is 20wt%～50wt%, the content of macroporous aluminium oxide be 35wt%～ 60wt%, the content of boehmite is 10wt %～30wt%.

The most in accordance with the method for claim 1, it is characterised in that in a described anti-hydrogenation catalyst, organic polycarboxylic acid Content is 0.10～0.35g/g FeOOH.

The most in accordance with the method for claim 1, it is characterised in that in a described anti-hydrogenation catalyst, molecular sieve is that Y type divides Son sieve and/or beta-molecular sieve, above-mentioned molecular sieve all uses hydrogen type molecular sieve.

The most in accordance with the method for claim 7, it is characterised in that described Y type molecular sieve character is as follows: SiO₂/Al₂O₃Mol ratio It is 10～15；Described beta-molecular sieve character is as follows: SiO₂/Al₂O₃Mol ratio is 40～80.

The most in accordance with the method for claim 1, it is characterised in that the character of a described anti-hydrogenation catalyst is as follows: pore volume is 0.50～1.00mL/g, specific surface area is 150～300m²/ g, catalyst granules is microspheroidal, a diameter of 0.1～0.8mm, mill Consumption rate≤2.0wt%, pore size distribution is as follows: the bore dia pore volume in the hole of 10nm～50nm accounts for the 10%～50% of total pore volume.

The most in accordance with the method for claim 1, it is characterised in that the character of a described anti-hydrogenation catalyst is as follows: pore volume is 0.40～0.90mL/g, specific surface area is 150～250m²/ g, pore size distribution is as follows: bore dia is at the pore volume in the hole of 10nm～50nm Account for the 20%～40% of total pore volume.

11. in accordance with the method for claim 1, it is characterised in that in two described anti-hydrogenation catalysts, with the weight of catalyst On the basis of amount, its composition is as follows: the content of FeOOH is 30wt%～60wt%, the content of macroporous aluminium oxide be 20wt%～ 50wt%, the content of binding agent is 3wt %～15wt %.

12. in accordance with the method for claim 1, it is characterised in that in two described anti-hydrogenation catalysts, organic polycarboxylic acid Content be 0.10～0.35g/g FeOOH.

13. in accordance with the method for claim 1, it is characterised in that in two described anti-hydrogenation catalysts, binding agent is poly-second Glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine, methylcellulose one or more.

14. in accordance with the method for claim 1, it is characterised in that the character of two described anti-hydrogenation catalysts is as follows: compare table Area is 150～300m²/ g, pore volume is 0.35～0.70mL/g, and bore dia at least accounts for always at the pore volume shared by the hole of 5～15nm The 60% of pore volume, catalyst granules is microspheroidal, a diameter of 0.1～0.8mm, rate of wear≤2.0wt%.

15. in accordance with the method for claim 1, it is characterised in that a described anti-hydrogenation catalyst or two anti-middle hydrogenation catalysts In agent, the character of macroporous aluminium oxide is as follows: specific surface area 160～250m²/ g, pore volume 0.80～1.20mL/g, average pore diameter For 13nm～25nm.

16. in accordance with the method for claim 1, it is characterised in that a described anti-hydrogenation catalyst or two anti-middle hydrogenation catalysts In agent, containing one or more of adjuvant component P, B, Si, F in macroporous aluminium oxide, in terms of element, adjuvant component is in the catalyst Weight content be 0.1%～5.0%.

17. in accordance with the method for claim 1, it is characterised in that a described anti-hydrogenation catalyst or two anti-hydrogenation catalysts In, organic polycarboxylic acid is one or more in citric acid, malic acid, tartaric acid.

18. according to the arbitrary described method of claim 5～16, it is characterised in that a described anti-hydrogenation catalyst or two counter is hydrogenated with In catalyst, the granularity of FeOOH is below 30 microns.

19. according to the arbitrary described method of claim 5～16, it is characterised in that a described anti-hydrogenation catalyst or two counter is hydrogenated with In catalyst, the granularity of FeOOH is 5～20 microns.