CN1238471C

CN1238471C - Method for producing fuel distillate

Info

Publication number: CN1238471C
Application number: CNB018236286A
Authority: CN
Inventors: 尤里·阿列克谢耶维奇·卡纳塔耶夫; 米哈伊尔·康斯坦丁诺维奇·尤林; 叶夫根尼·亚历山德罗维奇·鲁日尼科夫
Original assignee: PANJEHILL HOLDINGS CORP
Current assignee: PANJEHILL HOLDINGS CORP
Priority date: 2001-07-12
Filing date: 2001-07-12
Publication date: 2006-01-25
Anticipated expiration: 2021-07-12
Also published as: WO2003010259A1; GB2393731A8; GB2393731B; US20040238406A1; GB2393731A; CN1545547A; GB0402417D0

Abstract

The present invention relates to production of fuel distillates, which can be used for oil refining industry of producing engine fuel and jet fuel. The present invention has the idea that raw residual oil materials (tail fraction of fuel oil, tar oil and petroleum) is mixed with slate coal which is provided with 45 to 60 wt% of inorganic components and 40 to 55 wt% of organic components, and shale oil of which the weight of raw materials is from 1.0 to 6.0% and the hydrogen content is not less than 10 wt%. Then the obtained mixture is homogenized in a mixer which is not below 80 DEG C, and thermal inversion or hydrocracking is implemented to the mixture. The fuel distillates (gasoline, diesel oil and vacuum gas oil) are extracted from the product of thermal inversion or hydrocracking.

Description

Produce the method for fuel distillate

Technical field

The present invention relates to the petroleum refining industry field, more specifically relate to and be used for by thermal transition and produce the method that fuel distillate distills heavy still bottoms use for the hydrocracking of body dissolving agent process.

Background technology

Along with the consumption of world's oil and oil production now increases day by day, petroleum refining industry is towards deeply oil refining development.This task is only goed deep into the refining heavy hydrocarbon feeds by the emerging and economic favourable technology of extensive implementation and is solved, and heavy hydrocarbon feeds comprises bituminous matter and heavy metal (vanadium and nickel), for example oil fuel, tar, heavy oil (viscid bitumen), rock asphalt.

Solving one of promising and the most modern mode of this task is to make up the mixture of cracking residual feedstocks and coal by thermal transition or method for hydrogen cracking, and the amount that the latter adopts is 5～30% (RU, A1 No.2009162,1994 of Residual oil weight; US, A1 No.4544479,1985; RU, A1 No.2076871,1997).

According to known method, described mixture is accepted thermal transition (viscosity breaking) and is obtained to have than low viscosity and the product that reduces the heavy metal amount.This raw material and overhead product thereof can be reprocessed into the light fuel overhead product by catalytic cracking.

It is immaculate that this solution is not considered to.Therefore, the metal removal of relative low degree can not eliminated the difficulty of this process product of catalytic cracking subsequently; But even use the modern catalysts to stabilized metal also to need to increase consumption, and this can influence the general economic parameters of this known workaround unfriendly.

The another kind that solves described task is known and applicable method is the heavy oil feedstock unifining process (US, A1 No.5,972,202,1999) that has additional granularity control.The advantage of this process is that technology is flexible, promptly by modification process parameter (temperature, pressure, volumetric flow rate etc.), can realize the maximum conversion rate and the productive rate of desired product.

The shortcoming of this process is to use quite expensive catalysis system, for example ferric sulfate, other metallic sulfide, ironic hydroxide etc., and this can influence the technology and the economic parameters of this process unfriendly.

The method of producing fuel distillate from residual feedstocks is well known in the art, this method comprises mixes, implements thermal transition or the hydrocracking mixture of gained thus with residual feedstocks and sapropelinite and liquid aromatic additive, and separate required product (RU at last, A1 No.2076891,1997; RU, A1 No.2057786,1996).

In known method, under the temperature and pressure that raises, use thermal transition or hydrocracking to comprising heavy oil feedstock (oil fuel, tar, the western oil in siberian, Buzatchi and Mahgyshilak oil field heavy oil), Leningrad (Leningrad), the Baltic Sea, sulphur resinous shale or the Kuzbass sapromixite of sapropelinite-1～10 weight %, the crude shale oil of 1～10 weight % and 220～340 ℃ cut thereof or the mixture of naphthane and alkyl derivative thereof, separate fuel distillate subsequently.The productive rate of fuel distillate and reaches 90% of raw material weight when using thermal transition in the scope as raw material weight 55～60% when using hydrocracking.When using the hydrogenation refining process, the overhead product that thermal transition or hydrocracking are produced can be produced light duty engine fuel by reprocessing, comprises engine gasoline and diesel oil fuel.

The shortcoming of currently known methods is that they use so-called " crude shale oil " as aromatic additive and naphthane and alkyl derivative thereof.

This with use in the currently known methods " crude shale oil " industrial be to vaporize to produce by shale to be condition.The quality of thus obtained crude shale oil can not satisfy the needs to the fluid additive that uses as thermal transition or hydrocracking heavy oil feedstock process activator fully, because crude shale oil comprises in a large number the oxygenatedchemicals (phenol) of (reaching 13% volume) and reaches 0.5% mechanical impurity.

Naphthane comprises condensed aromatics, mainly is that the industrial goods of naphthalene and alkyl derivative thereof are produced by hydrogenation.The process of preparation naphthane and alkyl derivative thereof is very expensive.Correspondingly, finished product also is quite expensive.

Immediate with the present invention is the method for following production fuel distillate: this method comprises mixture and the thermal transition or the hydrocracking of the sapropelinite that mixes residual feedstocks and grinding and liquid activating additive, homogenizing gained, separating obtained subsequently product (RU, A1 No.2128207,1999).In known method, the hydrogenated fractions of boiling point in 300 to 400 ℃ of scopes is used as the liquid activating additive with 1～5 weight % amount.The productive rate of fuel distillate is 55～60 weight % when using thermal transition, and reaches 90 weight % when using hydrocracking.The shortcoming of this known arrangement is, the hydrogenated fractions that the use boiling point is 300 to 400 ℃ has also increased the cost of finished product as aromatic additive, because in order to ensure the higher hydrogen donor character of 300 to 400 ℃ of hydrogenated fractions of boiling point, additional fractionation by distillation stage and further hydrogenation refining are that production is necessary.

The quite expensive overslaugh of 300 to 400 ℃ of hydrogenated fractions of boiling point in petroleum refining industry, use this currently known methods.

Description

Target of the present invention is to improve the efficient of refining heavy still bottoms method, comprises the cost that reduces finished product.Technical result of the present invention is eliminate to use boiling point 300 to 400 ℃ hydrogenated fractions, and has kept the throughput of this method.

Described technical result is due to the fact that and realizes: the method for producing fuel distillate comprises sapropelinite and the liquid activating additive that mixes residual feedstocks and grinding, homogenizing is also implemented the thermal transition or the hydrocracking of gained mixture, and separate the product of wishing subsequently, the sapropelinite that grinds before the homogenizing is by mechanical activation at least a dispersion mixer, the slaty coal that comprises 45～60 weight % inorganic parts and 40～55 weight % organic moiety is as sapropelinite, evaporation of 200 to 400 ℃ of scopes and the shale oil that comprises at least 10.0 weight % hydrogen are as the liquid activating additive, and the consumption of described slaty coal and shale oil cut (weight percentage of raw material) is respectively from 1 to 5 and from 1.0 to 6.0.

In addition, use 3～15 gram molybdenums, 20～35 gram nickel, 3～10 gram cobalts, 30～40 gram chromium, 15～40 gram copper and the plumbous slaty coal of 5～20 grams of comprising per ton.

In addition, use the following slaty coal of inorganic part, weight percentage:

SiO ₂ 30～40 CaO 25～40 Na ₂O 0.3～3.0

Fe ₂O ₃ 5～10 MgO 1.5～5.0 P ₂O ₅ 0.1～0.7

Al ₂O ₃ 8～15 SO ₃ 1.5～5.0

TiO ₂ 0.5～0.7 K ₂O 2.0～5.0

In addition, carry out in the mixing tank of homogenizing under 80 to 100 ℃ temperature.

In addition, in the mechanical activation stage, the slaty coal quilt adds and is ground to granularity is 30 to 100 microns.

Mechanical-chemical is handled and is implemented in known Desi-14 type device and known dispersion mixer (homogenizer) and homogeneous phase mixing machine.

Other additional embodiment is possible, and wherein mixture is by twice homogenizing.

According to the present invention, heavy oil feedstock (oil fuel, tar) mixes continuously with liquid activating additive and sapropelinite, and wherein to be ground to granularity in advance be 30 to 100 microns (preferably 50 to 100 microns) to sapropelinite (slaty coal).

For activating additive being dispersed in the whole starting material, the gained mixture mixes and strong homogenizing.

At the abrasive solid activating additive with subsequently in the process of homogenizing 3 component mixtures, starting material have been realized quite effectively activation, and wherein (molecular size of 0.3～0.5 nanometer and heavy oil feedstock (0.4～0.7 nanometer) matches the size of additive.This is very important for producing activating additive with the condition that the intermolecular optimum of starting material contacts.

Starting material after this processing can be accepted thermal transition and hydrocracking under the condition of comparing not too strictness with currently known methods: promptly under from 415 to 440 ℃ temperature of reactor, effusive raw material temperature is 450 to 490 ℃ from stove, pressure is 4 to 10MPa, and volumetric flow rate is 0.8/ hour to 2.0/ hour.But most important aspect is thermal transition and hydrocracking process also can carry out without expensive catalysts.

" thermal transition " used among the present invention or the notion of hydrocracking have traditional implication, and comprise the cracked starting material are contacted with hydrogen, the liquid raw material of each unit volume uses 500～2, (T=0 ℃ of 000 unit volume standard conditions, P=0.1013MPa) hydrogen under or hydrogen-containing gas, pressure is 4.0～15.0MPa, and volume flow 1～3/ hour (be 20～90 minutes duration of contact) and temperature are 390～440 ℃.

In the experimental verification of technology, use and have the process furnace of finned tube and the non-reactor heating of hollow.Under the laboratory condition, promptly at pressurized vessel with have the data that obtain in the Continuous Flow device of 600 liters of reactor volumes and can be used for throughput by simulation well and reach 420 cubic metres of raw-material equipment and carry out the production of technical grade.

Optimal conditions (temperature, pressure, volumetric flow rate) can obtain the maximum finished product for those under this condition, and does not especially observe the condition that undesirable a large amount of coke forms in tube furnace and reactor.Keep preset time in reactor assembly after, cracked product is cooled and separates, and extracts required product simultaneously.Separation method commonly used is decompression (comparing with reaction conditions) evaporation; Separating liquid product from cream mud (enriched material of solid phase prod) can be by any known method, and for example centrifugal, filtration waits and implements; The steam product of separating liquid and reaction etc.We use the centrifugal method of using settling centrifuge.

Should be noted that thermal transition or hydrocracking under optimal conditions, form the coke produced that total amount reaches 5 weight %, it can not deposit on the wall of reaction unit, but removes from reactor with hydride.

The theory of known solid activating additive organic substance failure mechanisms has formed the basis of process of the present invention.Under optimal conditions, the decomposition of additive organic substance and liquefaction have formed the free radical with different molecular weight, and comprise the product liquid with hydrogen donor character compound in forming, and they are the tetrahydrochysene derivative of condensed aromatics, the derivative of nitrogenous and oxygen.

According to the chain free radical mechanism, these chemical active compounds that form from the solid additive organic substance in the hydrocracking process condition have guaranteed the destruction as the high boiling hydrocarbon that comprises in heavy still bottoms (oil fuel, the tar) composition, and contribute to the hydrogenation reaction of development material compound and degradation production thereof.

Fluid additive also has hydrogen donor character.The specific catalytic affect that initial raw materials and degradation production thereof are transformed applies by the inorganic part of additive, and its inorganic part is made of the silico-aluminate and the molysite of significance degree.

The for example hydrocracking of tar in the presence of the solid activating additive, and when the degree of depth of tar higher hydrocabon destruction, raw-material desulfurization, it comprised bitum destruction, the deposition of the coke produced that may form and solid activating additive inorganic part vanadium and nickel also.The slaty coal that comprises inorganic part (45～60 weight %) and organic moiety (40～55 weight %) can be used as sapropelinite.Especially, use and to comprise (gram number per ton) 3～15 gram molybdenums, 20～35 gram nickel, 3～10 gram cobalts, 30～40 gram chromium, 15～40 gram copper and the plumbous slaty coal of 5～20 grams.

In addition, the inorganic part of slaty coal is following, weight percentage:

SiO ₂ 30～40 CaO 25～40 Na ₂O 0.3～3.0

Fe ₂O ₃ 5～10 MgO 1.5～5.0 P ₂O ₅ 0.1～0.7

Al ₂O ₃ 8～15 SO ₃ 1.5～5.0

TiO ₂ 0.5～0.7 K ₂O 2.0～5.0

When the share of inorganic part is lower than 45 weight %, the cracking reaction of starting material (for example tar) proceeds to insufficient degree far away, this can cause the reduction of required product (gasoline, diesel oil and gas oil fraction) productive rate and increased once pass through in unconverted raw-material amount.

When the share of inorganic part surpassed 60% the limit, the cracking reaction that produces required product had formed unwanted gaseous state and coke shape product more.Therefore, the productive rate of required fuel distillate has also reduced.Because the corrosive nature of slaty coal inorganic part on reaction unit (process furnace of heating raw materials, reactor, the heat exchanger) wall, also reduced the work-ing life of device.

Any this class starting material-oil fuel, tar, heavy oil, rock asphalt.

Evaporation of 200 to 400 ℃ of scopes and the shale oil that comprises at least 10.0 weight % hydrogen are used as the liquid activating additive.This shale oil is produced by known method, promptly uses solid thermal carriers thermal treatment slaty coal.According to known method, fine grain slaty coal is dried and accepts the heat collapse of solidification heat carrier, forms gas-vapour mixture.The latter sprays with condensing mixt after doing cleaning, and removes first condensation product of the last running of deoiling.After this, gas-vapour mixture cools off in condenser, and second condensation product of oily last running is removed as end product.The uncooled part of gas-vapour mixture is separated in cracking fractionator, and the lighting end of oil is separated and remove as end product.This method can obtain its valuable cut with low levels mechanical impurity from slaty coal, and optimization process parameter (referring to " The Chemistry and Technology of Shale Oil ", Ed.By N.I.Zelenin, " Khimiya " Publishers, Leningrad, 1986, p.146).

Specifically being characterized as of the shale oil cut of from 200 to 400 ℃ of the boiling points of gained thus, owing to there is the obviously hydrogenated derivatives of amount, its composition of polycyclc aromatic compound comprises the hydrogen (at least 10 weight %) of raising amount.These compounds are by the hydroaromatic compounds of 2～4 rings (naphthalene, anthracene, phenanthrene, benzanthrene, pyrene, fluoranthene, in the wrong two, four and six derivatives) representative.This cut that boiling point is from 200 to 400 ℃ is hydrogen donor quite efficiently thermal transition and hydrocracking residual feedstocks (preferably tar).In order to obtain the required product of requirement by thermal transition or hydrocracking, the optimum content of hydrogen should be at least 10 weight % the shale oil that boiling point is from 200 to 400 ℃.If the amount of hydrogen is reduced to the value that is lower than 10 weight % in the shale oil, the productive rate of fuel distillate significantly reduces in thermal transition and the hydrocracking process.The amount of hydrogen is increased to the above value of 12 weight % in the shale oil can not influence the productive rate of fuel distillate, but can make finished product more expensive.Amount with oily raw material weight 1.0 to 6.0% is introduced the shale oil that at least 10.0 weight % hydrogen are evaporated and comprised to 200 to 400 ℃ of scopes.

Use hydrogen as liquid give body can very big reduction hydrocracking process in the hydrogen consumption of gas phase.On the data basis that obtains during the commerical test author to have set up the hydrogen consumption of reaction be 0.7～0.9% of raw-material weight.In thermal conversion processes, hydrogen only consumes to the body from slaty coal and hydrogen liquid.Compare with known method, the reduction of hydrogen consumption has positive influence to the technology and the economic parameters of the inventive method, specifically makes finished product cheap.

When only in the presence of slaty coal or shale oil, implementing thermal transition or hydrocracking, also can realize the result that some is positive.But in both cases, the productive rate of light oil products significantly reduces, because reactive system does not have the hydroaromatic compound with hydrogen donor character of necessary amounts.

In order to realize the light oil products of required productive rate, the essential amount that increases slaty coal is to raw-material 10～12%, perhaps uses " Kerogen 70 " or " Kerogen 90 " type (raw-material weight 4～6%) cleaning slaty coal.The amount of the shale oil of 200 to 400 ℃ of scope evaporations should be increased to 3.5～6% of raw-material weight.Any increase of slaty coal or shale oil mass all causes higher tooling cost.

When heat of dissociation transforms and during the product of hydrocracking, required fuel distillate is the extensive fuel fraction of using always: the diesel oil distillate of the gasoline fraction of 40～180 ℃ of scope evaporations, 180～360 ℃ of scope evaporations and 360～500 ℃ of gas oil fraction that scope is evaporated according to the present invention; Their character and using method are known for the professional in oil refining field.

The fuel distillate of producing can be refined into commercial fuel component or commercial fuel again by oil refining method commonly used in the industry.For instance, gasoline fraction can be accepted the hydrogenation refining under special-purpose catalyst, thereby produces the gasoline component with octane value 82～93 under research method.Diesel oil distillate can be as the commercial diesel fuel with cetane value 48～50 after the hydrogenation refining.

This diesel oil distillate is the main products when implementing process of the present invention.They are easy to be refined into commercial fuel again, i.e. the present invention can access unconspicuous result in the state of this area.

Description of drawings

Figure 1 shows that the schema of embodiment of the present invention.

Embodiment

Carrying out the installations and facilities scheme of the inventive method represents in the accompanying drawings.Arrive deposit from the slaty coal particle of bulk (being received) slaty coal of 25～250 millimeters sizes of rail vehicle or 0～25 millimeter size.From here, slaty coal is supplied to slaty coal hopper 1.Slaty coal can be transported to hopper 1 from the deposit field by truck or travelling belt.

Slaty coal from hopper is fed on the travelling belt, delivers on the crusher that has filter bag 2, is broken into 8 millimeters granularity there.8 millimeters slaty coal particle is transported in " Desi 14 " crusher 3, and slaty coal is obtained 1 millimeter-sized particles by further broken there.Behind " Desi 14 " crusher, for final grinding, the slaty coal after the fragmentation is added on " Desi 14 " pulverizer 4 by discharge-channel, is ground to the granularity less than 100 microns there." Desi 14 " pulverizer is equipped with tornado dust collector, air filter, bag filter and star feeder.

Be added to by the discharge-channel of " Desi 14 " pulverizer from the grinding slaty coal of " Desi 14 " pulverizer and reach in 140 microns purpose riddles (jigger screen), be added to then in the interim storage bin 5.The slaty coal shredding unit has the control panel of band protection and starting device.Riddle is designed to separate the slaty coal particle that size surpasses 140 microns.

Then, the slaty coal that grinds to form 100 micron granularities is added to the raw material preparing part.This stage is very important for the whole process of production chain.Raw material preparing is following carries out.Keeping under 80～100 ℃ the temperature, in the mixing tank of heating or another mixing device 9, adding shale oil in turn,, and adding slaty coal at last from the tar (or oil fuel) of storage tank 8 from storage tank 7.At first, in mixing device 9, add shale oil, from storage tank 8, add tar then, add slaty coal by measuring apparatus 6 again by pump.In order to prevent that slaty coal is deposited to the bottom of mixing tank, in the operation that adds three component mixture of raw material simultaneously, start mixing device.If mixing device can not be guaranteed the thorough mixing of 3 component mixtures, use pump to take out blender loader 10 in order to mix (all homogenizing) suggestion more fully.At this moment, in order to ensure the taking out property of tar, the temperature of raw material preparing part should maintain 80～100 ℃ level.

Behind mixing tank 9, the mixture of raw material of preparation is transported in the standby mixing tank 11, is added in the heat exchanger 13 by starting material high-pressure pump 12 therefrom, and is added to the starting material process furnace 14 from this.Process furnace 14 has two part-A and B.The temperature maintenance of A part is in 380～400 ℃ scope, and the temperature maintenance of furnace outlet depends on the type of raw materials of processing at 460～490 ℃.From process furnace, the starting material that part transforms be transported to the non-reactor heating 15 of hollow than lower part, raw-material there hydrocracking reaction carries out under the condition of 425～450 ℃ of hydrogen pressure 6～10MPa, volume flow 1.0～2.0/ hours and height for reactor temperature.Amount with 1,000～1,500 cubic metres of per 1 cubic metre of starting material adds hydrogen-containing gas (hydrogen content 80%).Behind reactor, gas-vapour mixture is directed in the heat exchanger 13, and in the heat separator 16 that further leads, and the there maintains under the pressure of 270～320 ℃ temperature and 10MPa.Under these conditions, mainly escape, and flow out in the bottom of heat separator with solid product at the cut of temperature evaporation more than 360～380 ℃ at the top of heat separator until the cut of 360～380 ℃ of temperature evaporations.The top air-flow of heat separator with by the hydrogen-containing gas behind the cooling system 17 in high-pressure separator 18 inner accumulated, hydrogen-containing gas separates with hydride there.Hydrogen-containing gas mixes with fresh hydrogen, is added to then in the recycle compressor 25.

Hydride from high-pressure separator feeds light pressure separator 19 and further arrives the accumulation jar by pipeline, is used for further refining.Arrive in water cooler 21 cooling than lower part (so-called " cream mud ") by flapper valve from heat separator, and come separation of liquid products and solid product to settling centrifuge 22 by pipe-line transportation.Product liquid (so-called " fugat ") mixes with hydride (top of heat separator), and after in process furnace 24, heating, mixture is added in the cracking fractionator 26 distillation, reaches 180 ℃ the gas oil fraction of 360～500 ℃ of diesel oil distillate, boiling points of 180～360 ℃ of gasoline fraction, boiling points and boiling point in the Residual oil more than 500 ℃ (circulation) thereby produce boiling point.

Solid product (cream mud) is collected in receptor 23, is fed to then and produces the pitch that uses on the asphalt production equipment in building the road, perhaps as the starting material that therefrom extract vanadium, nickel or rare earth metal.

The another kind that must note production scheme changes-does not have heat separator-also be possible.In the case, behind the reactor, air communication over-heat-exchanger 13, water cooler 17, high-pressure separator 18, light pressure separator 19 and settling centrifuge 22.

Advantages the following examples of the present invention are set forth.

In the embodiment that quotes, use tar from western siberian oil mixt as residual charge stock, it has following feature: density-984kg/m ³, elementary composition, weight percentage: C-86.8; H-10.86; S-1.5; N-0.3 (residue of oxygen and impurity-100), viscosity-28.0sSt, coking ability-10.0 weight %, bituminous matter-9.3 weight %, be lower than under 500 ℃ of temperature evaporation-24.5 weight %, the vanadium-140g/t that comprises, nickel-70g/t.

The Baltic slaty coal that use is received is as sapropelinite, and it has following feature, weight percentage: A ^d-46.70; CO ^d _2min-8.32; C ^Daf-81.3; H ^Daf-9.25; N ^Daf-0.28; S ^d _t-0.90; W ^d-3.0.

Use shale oil as the liquid activating additive, it is made of the cut that evaporates in 200 to 400 ℃ of scopes and has following feature: density-995kg/m ³, specific refractory power-1.5696, molecular weight-290, asphalt content-3.8 weight %, elementary composition, weight percentage: C-82.95; H-10.0; S-0.6; 14.9sSt during yield point-less than 20 ℃, viscosity-50 ℃.

The thermal transition of tar or hydrocracking process are implemented in the continuous flow apparatus that has 6 liters of reactors, perhaps implement in the industrial equipments with 10 cubic metres of reactors.The condition of thermal transition is: 425～450 ℃ of temperature, pressure (pressure of nitrogen, inherent appropriate hydrocarbon gas, hydrogen-containing gas) 3～5MPa, volumetric flow rate 1.0～2.0/ hours, 600～800 liters of every liter of starting material of gas circulation.The condition of hydrocracking is: 425～450 ℃ of temperature, pressure (hydrogen or hydrogen-containing gas) 6.0～10.0MPa, volumetric flow rate 1.0～2.0/ hours, 1,000～1,500 liters of every liter of starting material of gas circulation.

The amount of liquid aromatic additive is 0.5～6.0% of a tar weight, and the amount of sapropelinite is 0.5～5.0% of a tar weight.

In this process, take gas and product liquid away, and the separate solid component.The product liquid of this process is distilled into boiling point and reaches 180 ℃, 180～360 ℃, 360～500 ℃ cut and boiling point at the Residual oil more than 500 ℃.

The slaty coal of thermal transition or hydrocracking process and oil mixt prepare with the shale oil cut of 200～400 ℃ of Residual oils (particularly tar), boiling point and the slaty coal of being received by continuous combination thermal cracking.Be blended in the heating mixer that temperature is not less than 85 ℃ and carried out 2.5 hours, accept homogenizing in prepared then mixture decollator device or the processing activated equipment and handle.

Mixture so prepares, and can not end in long-time.

Embodiment 1

Basic mixture is that 200 to 400 ℃ shale oil cut prepares by the boiling point that mixes 10 tons of tar, 0.2 ton of slaty coal (inorganic part content is 40 weight %) and 0.3 ton.Be blended in the heating mixer that temperature is not less than 85 ℃ and carried out 2.5 hours, mixture is accepted activation and homogenizing then.Thermal transition is carried out under 1～2/ hour at pressure 3～5MPa, 425～450 ℃ of temperature, volumetric flow rate.The gained product liquid carries out centrifugal, thus separate solid.Product liquid is distilled into boiling point and reaches the cut of 180 ℃ (gasoline), 180～360 ℃ (diesel oil), 360～500 ℃ (gas oils) and boiling point at the Residual oil more than 500 ℃.Process parameter provides in table 1.

Embodiment 2

Except the content of slaty coal inorganic part is the 45 weight %, similar among starting material and thermal conversion processes condition and the embodiment 1.The thermal conversion processes parameter provides in table 1.

Embodiment 3

Except the content of slaty coal inorganic part is the 50 weight %, similar among starting material and thermal conversion processes condition and the embodiment 1.The thermal conversion processes parameter provides in table 1.

Embodiment 4

Except the content of slaty coal inorganic part is the 60 weight %, similar among starting material and thermal conversion processes condition and the embodiment 1.The thermal conversion processes parameter provides in table 1.

Embodiment 5

Except the content of slaty coal inorganic part is the 65 weight %, similar among starting material and thermal conversion processes condition and the embodiment 1.The thermal conversion processes parameter provides in table 1.

Embodiment 6

Basic mixture is that 200 to 400 ℃ and hydrogen content are that the shale oil cut of 10 weight % prepares by the boiling point that mixes 10 tons of tar, 0.2 ton of slaty coal and 0.3 ton.Be blended in the heating mixer that temperature is not less than 85 ℃ and carried out 2.5 hours, mixture is accepted activation and homogenizing then.Slaty coal content is 0.5 weight % in the present embodiment.

Thermal transition is at pressure 3～4MPa, 430～450 ℃ of temperature, and volumetric flow rate was carried out under 1～2/ hour.The product liquid of gained carries out the centrifugal separate solid component of coming.Product liquid is distilled into boiling point and reaches the cut of 180 ℃ (gasoline), 180～360 ℃ (diesel oil), 360～500 ℃ (gas oils) and boiling point at the Residual oil more than 500 ℃.Process parameter provides in table 2.

The product of gained has following feature: boiling point reaches 180 ℃ gasoline fraction: specific refractory power 1.4216; Elementary composition, weight percentage: C 84.53, H 13.57, and S 0.46, and N 0.06; The diesel fuel fractions that boiling point is 180～360 ℃: specific refractory power 1.4786; Elementary composition, weight percentage: C 85.89, H 12.26, and S 0.69, and N 0.06; The gas oil fraction that boiling point is 360～500 ℃: specific refractory power 1.5211; Elementary composition, weight percentage: C 86.60, H 11.24, S1.29, N 0.21; Boiling point is at the residual oil fraction more than 500 ℃: density 1,011kg/m ³, elementary composition, weight percentage: C 88.18, H 9.48, and S 1.70, and N 0.64.

Embodiment 7

Except the add-on of slaty coal is the 1.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 8

Except the add-on of slaty coal is the 2.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 9

Except the add-on of slaty coal is the 3.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 10

Except the add-on of slaty coal is the 5.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 11

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 0.5 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 12

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 1.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 13

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 2.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 14

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 3.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 15

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 6.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 16

Except the amount of slaty coal is the 2.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 2.

Embodiment 17

Embodiment 18

Basic mixture is by mixing 7.5 tons of tar, and 2.5 tons of boiling points prepare at the shale oil of the turning oil more than 500 ℃, 0.2 ton of slaty coal and 0.3 ton.Be blended in the heating mixer that temperature is not less than 85 ℃ and carried out 2.5 hours, mixture is accepted activation and homogenizing then.The inorganic part content of slaty coal is 40 weight % in the present embodiment.

Carry out under 1～2/ hour at pressure 6～10MPa, 430～450 ℃ of temperature, volumetric flow rate with slaty coal and the cracking of shale oil blended hydrogenation of tar, and the ratio of hydrogen-containing gas and tar is 1,000～1 500Sm ³Gas ratio 1m ³Raw material.

The product liquid of centrifugal gained comes the separate solid component.Hydride is distilled into boiling point and reaches the cut of 180 ℃ (gasoline), 180～360 ℃ (diesel oil), 360～500 ℃ (gas oils) and boiling point at the Residual oil more than 500 ℃.Boiling point is returned at the Residual oil more than 500 ℃ and is used for hydrocracking, and mixes with basic tar.

The product of gained has following feature: boiling point reaches 180 ℃ cut: specific refractory power 1.4728; Elementary composition, weight percentage: C 86.25, H 12.20, and S 1.26, and N 0.07; The cut that boiling point is 180～360 ℃: specific refractory power 1.728; Elementary composition, weight percentage: C86.25, H 12.20, and S 1.26, and N 0.07; The cut that boiling point is 360～500 ℃: specific refractory power 1.5305; Elementary composition, weight percentage: C 85.95, H 11.13, and S 1.86, and N 0.31; Boiling point is at the Residual oil more than 500 ℃: density 1,000kg/m ³, coking ability 6.5%, asphalt content 6.3%, content of vanadium 300g/t, nickel content 130g/t, elementary composition, weight percentage: C88.08, H 9.50, and S 1.70, and N 0.62.

Embodiment 19

Except the content of slaty coal inorganic part is the 45 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 3.

Embodiment 20

Except the content of slaty coal inorganic part is the 50 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 3.

Embodiment 21

Except the content of slaty coal inorganic part is the 60 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 3.

Embodiment 22

Except the content of slaty coal inorganic part is the 65 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 3.

Embodiment 23

Except the amount of slaty coal is the 0.5 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 24

Except the amount of slaty coal is the 1.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 25

Except the amount of slaty coal is the 2.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 26

Except the amount of slaty coal is the 3.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 27

Except the amount of slaty coal is the 5.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 28

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 0.5 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 29

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 1.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 30

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 2.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 31

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 3.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 32

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 6.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 4.

Embodiment 33

Embodiment 34

Except the amount of the shale oil cut of 200 to 400 ℃ of boiling points is the 3.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 6.The hydrocracking process parameter provides in table 4.

Embodiment 35

Except the hydrogen richness of the shale oil cut of 200 to 400 ℃ of boiling points is the 8.0 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 5.

Embodiment 36

Except the hydrogen richness of the shale oil cut of 200 to 400 ℃ of boiling points is the 10 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 5.

Embodiment 37

Except the hydrogen richness of the shale oil cut of 200 to 400 ℃ of boiling points is the 12 weight %, similar among starting material and thermal conversion processes condition and the embodiment 6.The thermal conversion processes parameter provides in table 5.

Embodiment 38

Except the hydrogen richness of the shale oil cut of 200 to 400 ℃ of boiling points is the 8.0 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 5.

Embodiment 39

Except the hydrogen richness of the shale oil cut of 200 to 400 ℃ of boiling points is 10% weight, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 5.

Embodiment 40

Except the hydrogen richness of the shale oil cut of 200 to 400 ℃ of boiling points is the 12 weight %, similar among starting material and hydrocracking process condition and the embodiment 18.The hydrocracking process parameter provides in table 5.

Embodiment 41

According to RU patent 2128207 method of similar solution, prepared mixture comprises, weight percentage: tar-100.0, Baltic slaty coal-2.0 comprises inorganic part-1.3; Shale oil-3.0.Then, carry out thermally splitting under the condition below: temperature-425 ℃, pressure-4MPa, volumetric flow rate-1.0/ hour.Productive rate below having realized is in the tar weight percentage: gas-7.8, water-1.0, the cut that boiling point is 180～360 ℃-42.9, the cut that boiling point is 360～520 ℃-15.1, boiling point be at the Residual oil more than 520 ℃-22.5, the coke on the sapropelinite inorganic part-3.7.

Embodiment 42

According to RU patent 2128207 method of similar solution, prepared mixture comprises, weight percentage: tar-100.0, Baltic slaty coal-2.0 comprises inorganic part-1.3; Shale oil-3.0; Hydrogen consumes-2.5.Then, carry out thermally splitting under the condition below: temperature-425 ℃, pressure-10MPa, volumetric flow rate-1.0/ hour.Productive rate below having realized, in the tar weight percentage: gas-6.0, water-0.5, boiling point reaches 180 ℃ cut-19.0, the cut that boiling point is 180～360 ℃-63.0, the cut that boiling point is 360～520 ℃-11.0, boiling point be at the Residual oil more than 520 ℃-1.5, the coke on the sapropelinite inorganic part-6.5.

The embodiment of table 1 thermal conversion processes and slaty coal inorganic part magnitude relation

No.	The starting material inclusion, weight percentage	Embodiment
		Embodiment					1	2	3	4	5
		1	Tar	100.0	100.0	100.0	1	2	3	4	5	100.0	100.0
2	Slaty coal, the inorganic part that comprises	1	Tar	100.0	100.0	100.0	2.0 40	2.0 45	2.0 50	2.0 60	2.0 65	100.0	100.0
2	Slaty coal, the inorganic part that comprises	3	The shale oil cut that boiling point is 200～400 ℃	3.0	3.0	3.0	2.0 40	2.0 45	2.0 50	2.0 60	2.0 65	3.0	3.0
4	Process condition: temperature, ℃ pressure, the MPa volume flow, hour ^-1	3	The shale oil cut that boiling point is 200～400 ℃	3.0	3.0	3.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	3.0	3.0
4		5	Products collection efficiency, in the tar percetage by weight: the gas water boiling point reaches the coke on 180 ℃ the cut slate coal inorganic part of cut boiling point more than 500 ℃ of 360～500 ℃ of cut boiling points of 180～360 ℃ of cut boiling points	4.0 0.5 5.3 30.0 7.6 56.0 1.6	4.9 0.8 7.6 46.8 6.7 36.4 1.8	5.0 1.0 8.5 47.4 5.5 35.6 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	7.0 1.0 12.7 51.0 7.0 23.2 3.1	10.5 1.0 8.3 35.3 7.5 35.9 6.5

The embodiment of table 2 thermal conversion processes

No.	The starting material inclusion, weight percentage	Embodiment
		Embodiment												6	7	8	9	10	11	12	13	14	15	16	17
		1	Tar	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	6	7	8	9	10	11	12	13	14	15	16	17	100.0	100.0
2	Slaty coal, the inorganic part that comprises	1	Tar	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	0.5 0.3	1.0 0.6	2.0 1.2	3.0 1.8	5.0 3.0	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	- -	100.0	100.0
2	Slaty coal, the inorganic part that comprises	3	The shale oil cut that boiling point is 200～400 ℃	3.0	3.0	3.0	3.0	3.0	0.5	1.0	2.0	3.0	6.0	0.5 0.3	1.0 0.6	2.0 1.2	3.0 1.8	5.0 3.0	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	- -	-	3.0
4	Process condition: temperature, ℃ pressure, the MPa volume flow, hour ^-1	3	The shale oil cut that boiling point is 200～400 ℃	3.0	3.0	3.0	3.0	3.0	0.5	1.0	2.0	3.0	6.0	445 4.0 2.0	445 4.0 2.0	445 3.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 3.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	-	3.0
4		5	Products collection efficiency, in the tar percetage by weight: the gas water boiling point reaches the coke of the cut slate coal inorganic part of cut boiling point more than 500 ℃ of 360～500 ℃ of cut boiling points of 180 ℃ 180～360 ℃ of cut boiling points	4.5 0.9 6.2 35.7 7.5 46.2 2.5	5.3 1.0 8.1 47.9 6.3 33.0 2.4	7.0 1.0 12.7 51.0 7.0 23.2 3.1	7.8 1.0 13.6 54.2 8.3 16.8 4.3	10.8 1.0 8.5 38.5 5.3 36.9 7.0	4.8 0.8 5.8 34.3 8.0 46.5 2.3	4.9 0.9 7.7 45.7 8.5 32.6 2.7	6.5 1.0 11.8 47.9 8.8 24.4 3.6	7.0 1.0 12.7 51.0 7.0 23.2 3.1	7.5 1.0 13.2 52.3 9.0 21.0 4.0	445 4.0 2.0	445 4.0 2.0	445 3.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	445 3.0 2.0	445 4.0 2.0	445 4.0 2.0	445 4.0 2.0	6.0 1.0 5.3 35.5 7.0 43.0 4.2	6.1 1.0 5.6 33.7 8.6 43.5 4.5

The embodiment of table 3 hydrocracking process and slaty coal inorganic part magnitude relation

No.	The starting material inclusion, weight percentage	Embodiment
		Embodiment					1	2	3	4	5
		1	The recycle of tar boiling point more than 500 ℃	75 25	75 25	75 25	1	2	3	4	5	75 25	75 25
2	Slaty coal, the inorganic part that comprises	1	The recycle of tar boiling point more than 500 ℃	75 25	75 25	75 25	2.0 40	2.0 45	2.0 50	2.0 60	2.0 65	75 25	75 25
2	Slaty coal, the inorganic part that comprises	3	The shale oil cut that boiling point is 200～400 ℃	3.0	3.0	3.0	2.0 40	2.0 45	2.0 50	2.0 60	2.0 65	3.0	3.0
4	H consumes	3	The shale oil cut that boiling point is 200～400 ℃	3.0	3.0	3.0	0.7	0.8	0.8	0.9	1.5	3.0	3.0
4	H consumes	5	Process condition: temperature, ℃ pressure, the MPa volume flow, hour ^-1Ratio: hydrogen-containing gas/starting material, Sm ³/m ³	445 4.0 2.0 1,400	445 4.0 2.0 1,400	445 4.0 2.0 1,400	0.7	0.8	0.8	0.9	1.5	445 4.0 2.0 1,400	445 4.0 2.0 1,400
6	Products collection efficiency, in the tar percetage by weight: the gas water boiling point reaches the coke on 180 ℃ the cut slate coal inorganic part of cut boiling point more than 500 ℃ of 360～500 ℃ of cut boiling points of 180～360 ℃ of cut boiling points	5		445 4.0 2.0 1,400	445 4.0 2.0 1,400	445 4.0 2.0 1,400	6.2 0.9 18.1 53.4 13.0 9.0 4.4	6.0 1.0 19.0 56.1 13.5 5.5 3.9	6.3 1.0 20.6 60.7 12.4 1.6 3.2	6.8 1.0 21.0 60.3 11.7 1.7 3.4	11.6 0.8 12.0 58.0 15.1 2.5 6.5	445 4.0 2.0 1,400	445 4.0 2.0 1,400

The embodiment of table 4 hydrocracking process

No.	The starting material inclusion, weight percentage	Embodiment
		Embodiment												23	24	25	26	27	28	29	30	31	32	33	34
		1	Tar	75	75	75	75	75	75	75	75	75	75	23	24	25	26	27	28	29	30	31	32	33	34	75	75
The recycle of boiling point more than 500 ℃	25		Tar	75	75	75	75	75	75	75	75	75	75	25	25	25	25	25	25	25	25	25	25	25		75	75
The recycle of boiling point more than 500 ℃	25		2	Slaty coal, the inorganic part that comprises	0.5 0.3	1.0 0.6	2.0 1.2	3.0 1.8	5.0 3.0	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	25	25	25	25	25	25	25	25	25	25	25	2.0 1.2	2.0 1.2	- -
3	The shale oil cut that boiling point is 200～400 ℃	3.0	2	Slaty coal, the inorganic part that comprises	0.5 0.3	1.0 0.6	2.0 1.2	3.0 1.8	5.0 3.0	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	3.0	3.0	3.0	3.0	0.5	1.0	2.0	3.0	6.0	-	3.0	2.0 1.2	2.0 1.2	- -
3	The shale oil cut that boiling point is 200～400 ℃	3.0	4	Process condition: temperature, ℃ pressure, the MPa volume flow, hour ^-1Ratio: hydrogen-containing gas/starting material, Sm ³/m ³	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	3.0	3.0	3.0	3.0	0.5	1.0	2.0	3.0	6.0	-	3.0	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400
5	Products collection efficiency, in the tar percetage by weight: the gas water boiling point reaches the coke of the cut slate coal inorganic part of cut boiling point more than 500 ℃ of 360～500 ℃ of cut boiling points of 180 ℃ 180～360 ℃ of cut boiling points	5.4 0.8 17.8 53.4 11.1 10.5 4.5	4		445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400	5.9 1.0 17.8 54.9 11.8 8.8 3.8	6.3 1.0 20.6 60.7 12.4 1.7 3.2	7.1 1.0 21.3 59.7 12.7 1.6 3.5	10.9 0.9 11.3 59.0 18.2 3.0 5.9	5.8 1.0 8.9 47.7 17.5 18.2 4.2	6.0 0.9 10.0 48.5 18.0 16.4 4.0	6.5 1.0 18.3 57.1 16.9 1.7 3.4	6.3 1.0 20.6 60.7 12.4 1.7 3.2	7.2 1.0 21.4 60.9 13.4 1.5 3.6	5.7 1.1 8.0 42.6 13.0 27.1 4.5	5.8 0.9 10.0 40.0 7.7 32.7 5.9	445 10 2.0 1,400	445 10 2.0 1,400	445 10 2.0 1,400

The embodiment of table 5 thermal transition and hydrocracking process and shale oil hydrogen richness relation

No.	The starting material inclusion, weight percentage	Embodiment
		Embodiment								Thermal transition			Hydrocracking			41	42
		35	36	37	38	39	40			Thermal transition			Hydrocracking
		35	36	37	38	39	40	1	Tar	100.0	100.0	100.0	75.0	75.0	75.0			100.0	60.0
The recycle of boiling point more than 500 ℃	-	-	-	25.0	25.0	25.0	-		Tar	100.0	100.0	100.0	75.0	75.0	75.0	40.0		100.0	60.0
The recycle of boiling point more than 500 ℃	-	-	-	25.0	25.0	25.0	-		2	Slaty coal, the inorganic part that comprises	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	40.0	2.0 1.2	2.0 1.3	2.0 1.3
3	The shale oil cut that boiling point is 200～400 ℃, the hydrogen richness that comprises	3.0 8.0	3.0 10.0	3.0 12.0	3.0 8.0	3.0 10.0	3.0 12.0	3.0 8.5	2	Slaty coal, the inorganic part that comprises	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	2.0 1.2	3.0 8.5	2.0 1.2	2.0 1.3	2.0 1.3
3		3.0 8.0	3.0 10.0	3.0 12.0	3.0 8.0	3.0 10.0	3.0 12.0	3.0 8.5	4	Process condition: temperature, ℃ pressure, the MPa volume flow, hour ^-1Ratio: hydrogen-containing gas/starting material, Sm ³/m ³	445 4.0 2.0 -	445 4.0 2.0 -	445 4.0 2.0 -	445 10.0 2.0 1,400	445 10.0 2.0 1,400	3.0 8.5	445 10.0 2.0 1,400	445 4.0 1.0 -	445 10.0 1.0 1,000
5	Products collection efficiency, in the tar percetage by weight: the gas water boiling point reaches the coke of the cut slate coal inorganic part of cut boiling point more than 500 ℃ of 360～500 ℃ of cut boiling points of 180 ℃ 180～360 ℃ of cut boiling points	5.1 0.9 10.2 45.0 6.1 34.1 3.6	7.5 1.0 11.5 49.1 16.9 15.0 4.0	7.7 1.0 12.2 50.8 17.8 11.7 3.9	6.1 0.9 16.3 43.4 13.5 22.1 3.6	7.5 1.0 23.1 62.8 6.3 1.3 4.0	7.8 1.0 23.6 63.2 5.5 1.2 3.8	7.8 1.0 12.0 42.9 15.1 22.5 3.7	4		445 4.0 2.0 -	445 4.0 2.0 -	445 4.0 2.0 -	445 10.0 2.0 1,400	445 10.0 2.0 1,400	3.0 0.5 19.0 63.0 11.0 1.5 6.5	445 10.0 2.0 1,400	445 4.0 1.0 -	445 10.0 1.0 1,000

The data analysis that provides in the table 1 is as follows.Along with slaty coal inorganic part content is increased to 50 weight % from 40 weight %, the productive rate of fuel distillate is increased to 55.9 weight % (condition of embodiment 3) from 35.3 weight % (condition of embodiment 1) under the tar thermal transition, and slaty coal inorganic part content is increased to 60 weight % (condition of embodiment 4) and causes the gain in yield of fuel distillate to 63.7 weight % (condition of embodiment 4).But slaty coal inorganic part content further is increased to 65 weight % and does not cause the gain in yield of fuel distillate, but is reduced to 43.6 weight % (condition of embodiment 5).Worthless reaction-form a large amount of gaseous products (10.5 weight %) and coke (6.5 weight %)-in the condition of embodiment 5, produce.

Therefore, data show that technological achievement of the present invention is owing to the slaty coal inorganic part content that equals 45～60 weight % and owing to using the shale oil cut of 200～400 ℃ of boiling points to be achieved as the liquid activating additive with the amount of raw-material weight 3.0% in the comparing embodiment 2,3 and 4.40 and 65% slaty coal inorganic part content can not be guaranteed the realization of technological achievement in the tar thermal conversion processes.

The data analysis that provides in the table 2 is as follows.Embodiment 6～10 has set forth the present invention, and wherein slaty coal is used as the solid activating additive in the tar thermal transition.Tar content among the described embodiment (weight percentage) is: 0.5,1.0,2.0,3.0,5.0.The cut overall yield that boiling point reaches 180 ℃, 180～360 ℃ and 360～500 ℃ is 70.7～76.1 to the maximum (weight percentage, in tar, embodiment 8 and 9).When 5 weight % slaty coal content, the productive rate of fuel distillate is lower than 2.0 and 3.0% of tar weight.If slaty coal content is lower than 1.0 weight %, technological achievement of the present invention can not realize owing to reduced the productive rate of required product.Slaty coal content can not cause the increase of required product productive rate when surpassing 5% limit, and because the inefficient consumption of slaty coal and the cost of the tar thermal conversion processes finished product that only can raise.

Therefore, slaty coal should add with the amount of relative starting material 1.0～5.0 weight %.The amount of liquid activating additive should be 1.0～6.0% of tar weight.

Embodiment 11～15 has set forth the present invention, and its mid-boiling point is that 200 to 400 ℃ shale oil cut is used as the liquid activating additive.Content of additive described in the embodiment 11～15 (weight percentage) is respectively: 0.5,1.0,2.0,3.0 and 6.0% of tar weight.The cut overall yield that boiling point reaches 180 ℃, 180～360 ℃ and 360～500 ℃ is 68.5～70.7 (in the conditions of embodiment 13 and 14) to the maximum.When the liquid activating additive is 6.0 weight %, the productive rate of required product high slightly (being 74.5 weight % under the condition of embodiment 15).Boiling point is that 200～400 ℃ cut only can cause when surpassing 6% limit because the inefficient consumption of shale oil and the cost of the finished product that significantly raise.

Therefore, the hydrogen richness shale oil cut that is not less than 200～400 ℃ of the boiling points of 10.0 weight % should add with the amount of raw-material 1.0～6.0 weight %.

Embodiment 16 has set forth the slaty coal that only uses tar 2.0 weight % amount according to the invention process tar thermal conversion processes the time.The productive rate of the following three kinds of cuts of embodiment 16 conditions (boiling point reaches 180 ℃, 180～360 ℃, 360～500 ℃) is 57.8 weight %, calculates with tar.

Embodiment 17 has set forth the parameter of tar thermal conversion processes, and the shale oil cut of 200～400 ℃ of its mid-boiling points and hydrogen richness 10.0 weight % is as the liquid activating additive.The productive rate of required product is 47.9 weight % under embodiment 17 conditions, calculates with tar.

The data analysis that provides in the table 3 is as follows.Along with slaty coal inorganic part content is increased to 50 weight % from 40 weight %, the productive rate of fuel distillate is increased to 93.7 weight % (condition of embodiment 20) from 84.5 weight % (condition of embodiment 18) under the hydrogenation of tar cracking, and slaty coal inorganic part content be increased to 60 weight % (condition of embodiment 21) can not cause fuel distillate productive rate increase and be 93.0 weight % (conditions of embodiment 21).Slaty coal inorganic part content further is increased to 65 weight % and causes the productive rate of fuel distillate to be reduced to 85.1 weight % (condition of embodiment 22).Under these conditions, a large amount of hydrocarbon gas C of worthless reaction-formation ₁C ₄, H ₂S (11.6 weight %) and coke produced (6.5 weight %)-developed.

Therefore, the data in the comparing embodiment 18,20 and 21 show technological achievement of the present invention because the shale oil cut that use is equivalent to the slaty coal inorganic part content of 45～60 weight % and is not less than 10.0 weight % owing to amount 200～400 ℃ of boiling points of use and hydrogen richness with raw-material weight 3.0% is achieved as the liquid activating additive.40 and 65% slaty coal inorganic part content can not be guaranteed the realization of technological achievement in the hydrogenation of tar cracking process.

The interpretation of result that provides in the table 4 is as follows.Embodiment 23～27 has set forth the present invention, and wherein slaty coal is used as the solid activating additive in the hydrogenation of tar cracking.Tar content among the embodiment 23～27 (weight percentage) is: 0.5,1.0,2.0,3.0,5.0.The cut overall yield that boiling point reaches 180 ℃, 180～360 ℃ and 360～500 ℃ is 93.7 weight % in embodiment 25 and 26 to the maximum, calculates with tar.When 5 weight % slaty coal content, the productive rate of fuel distillate is lower than 2.0 and 3.0% of tar weight.If slaty coal content is lower than 1.0 weight %, technological achievement of the present invention can not realize owing to reduced the productive rate of required product.Slaty coal content can not cause the increase of required product productive rate when surpassing 5% limit, and because the inefficient consumption of slaty coal and the cost of the tar thermal conversion processes finished product that only can raise.

Embodiment 28～32 has set forth the present invention, and its mid-boiling point is that shale oil cut that 200～400 ℃ and hydrogen richness are not less than 10.0 weight % is used as the liquid activating additive in the hydrogenation of tar cracking.Content of additive is respectively described in the embodiment 28～32: 0.5,1.0,2.0,3.0 and 6.0 weight %, calculate with starting material.The cut overall yield that boiling point reaches 180 ℃, 180～360 ℃ and 360～500 ℃ is 92.3～93.7 (in the conditions of embodiment 30 and 31) to the maximum.When liquid activating additive content is 6.0 weight %, the productive rate of required product high slightly (being 95.7 weight % under the condition of embodiment 32).Boiling point is the cost that 200～400 ℃ cut only can cause the desired product because the inefficient consumption of shale oil has raise when surpassing 6% content limit, and the while, its gain in yield was not obvious.

Therefore, the shale oil cut that hydrogen richness is not less than 200～400 ℃ of the boiling points of 10.0 weight % should be added into the amount of 1.0～6.0 weight % in the Residual oil, calculates with starting material.

Embodiment 33 has set forth the slaty coal that only uses 2.0 weight % amount according to the invention process hydrocracking process time, calculates with tar.The productive rate of the following three kinds of cuts of embodiment 33 conditions (boiling point reaches 180 ℃, 180～360 ℃, 360～500 ℃) is 63.6 weight %, calculates with tar.

Embodiment 34 has set forth the parameter of hydrogenation of tar cracking process, and the shale oil cut that its mid-boiling point is 200～400 ℃ is used as the liquid activating additive by the amount with 3.0 weight %, calculates with tar.The productive rate of required product is 57.7 weight % under embodiment 34 conditions, calculates with tar.

The data analysis that provides in the table 5 is as follows.Embodiment 35,36 and 37 is setting forth the present invention aspect the tar thermal transition, and the shale oil cut of 200～400 ℃ of its mid-boiling points and hydrogen richness 8.0,10.0 and 12.0 weight % is used as the liquid activating additive.Embodiment 35 coal-tar middle oil hydrogen richnesss are 8.0 weight %, embodiment 36-10 weight %, embodiment 37-12 weight %.To reach the productive rate of 180 ℃, 180～360 ℃ and 360～500 ℃ cuts be 77.5 weight % to boiling point under embodiment 36 conditions, calculates with tar.

The hydrogen richness of shale oil cut is reduced to 8.0 weight % and causes the productive rate of required cut to be reduced to 61.3 weight % in embodiment 35 conditions, calculates with tar.

The hydrogen richness of shale oil cut is elevated to the remarkable increase (productive rate of required cut is 80.8 weight % in embodiment 37 conditions) that 12 weight % can not cause required cut productive rate in embodiment 37 conditions, and only can be owing to the raise cost of finished product of the inefficient consumption of shale oil.Therefore, 200～400 ℃ of boiling points and hydrogen richness 10～12 weight % add the shale oil cut amount should be 6.0 weight %.

Embodiment 38,39 and 40 is setting forth the present invention aspect the hydrogenation of tar cracking, and the shale oil cut of 200～400 ℃ of its mid-boiling points and hydrogen richness 8.0,10.0 and 12.0 weight % is used as the liquid activating additive.To reach the overall yield of 180 ℃, 180～360 ℃ and 360～500 ℃ cuts be 92.2 weight % to boiling point under embodiment 39 conditions, calculate with tar, and the consumption of hydrogen from gas phase is 1.0% of raw-material weight.

The hydrogen richness of shale oil cut is reduced to 8.0 weight % and causes the productive rate of required cut to be reduced to 73.2 weight % in embodiment 38 conditions.

The hydrogen richness of shale oil cut is elevated to the remarkable increase (productive rate of required cut is 92.3 weight % in embodiment 40 conditions) that 12 weight % can not cause required cut productive rate in embodiment 40 conditions.Therefore, 200～400 ℃ of boiling points and hydrogen richness be not less than 10 weight % add the shale oil cut amount should be 1.0～6.0 weight %.

From the inventive method embodiment 4,8,14,21,25,31,36,39 and represent similar approach (RU 2128207) 300～400 ℃ of boiling points hydrogenated fractions as the result of the embodiment 41 of activating additive and 42 relatively, can draw because use has the slaty coal of advising inorganic part content according to the present invention, 200～400 ℃ of boiling points and hydrogen richness are not less than the shale oil cut of 10.0 weight %, and homogenizing in mixing tank, can eliminate the hydrogenated aromatic additive that uses 300～400 ℃ of expensive boiling points, keep the product productive rate actually in level simultaneously with respect to tar 90～93 weight %.Machinery and chemical activation also cause product overall yield and prototype that certain increase is relatively arranged, and combine the hydrogen consumption in the time of can also reducing the hydrogenation of tar cracking with above-mentioned feature of the present invention.

Therefore, the present invention guarantees to have realized not conspicuous technological achievement in the prior art.

Industrial applicability

The present invention is successfully used to petroleum refining industry most and is produced fuel distillate, and it is the raw material of producing engine fuel and jet fuel.

Claims

1, a kind of method of producing fuel distillate, it comprises sapropelinite and the liquid activating additive that mixes residual feedstocks and ground, the mixture of homogenizing and thermal transition or hydrocracking gained, extract the expectation product subsequently, the sapropelinite that the method is characterized in that described grinding before homogenizing at least a dispersion mixer machinery and chemical activation, use comprises the slaty coal of 45～60 weight % inorganic parts and 40～55 weight % organic moiety as described sapropelinite, use 200 to 400 ℃ of scope evaporations and hydrogen richness to be not less than the shale oil cut of 10.0 weight % as the liquid activating additive, in starting material, the consumption of described slaty coal and shale oil cut is respectively 1.0～5.0 weight % and 1.0～6.0 weight %.

2, the method for claim 1 is characterized in that used slaty coal is per ton to comprise: 3～15 gram molybdenums, 20～35 gram nickel, 3～10 gram cobalts, 30～40 gram chromium, 15～40 gram copper and 5～20 grams are plumbous.

3, the method for claim 1 is characterized in that the weight percentage of used slaty coal inorganic part is as follows:

SiO ₂ 30～40 CaO 25～40 Na ₂O 0.3～3.0

Fe ₂O ₃ 5～10 MgO 1.5～5.0 P ₂O ₅ 0.1～0.7

Al ₂O ₃ 8～15 SO ₃ 1.5～5.0

TiO ₂ 0.5～0.7 K ₂O 2.0～5.0

4, the method for claim 1 is characterized in that homogenizing is to carry out in mixing tank under 80 to 100 ℃ temperature.

5, the method for claim 1 is characterized in that described slaty coal through machinery and chemical activation is ground to 30 to 100 microns granularity.