CN108463537A

CN108463537A - The method for handling heavy hydrocarbon feeds

Info

Publication number: CN108463537A
Application number: CN201680075375.1A
Authority: CN
Inventors: 伊维诺维奇·多马诺夫; 弗拉迪米尔·瓦西里维奇·罗曼科夫; 瓦迪姆维克托罗维奇·斯塔涅尼科夫
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-12-24
Filing date: 2016-11-10
Publication date: 2018-08-28
Also published as: WO2017111764A1; CO2017013225A2; EA035887B1; US20180371329A1; RU2018121020A3; CA3009626A1; BR112018012882A2; MX2018007689A; PE20181211A1; EA201891513A1; RU2018121020A

Abstract

One kind is used to handle heavy hydrocarbon feeds, the mainly method of heavy crude, including：With preset pressure pretreated feedstock and secondary gas mixture, pretreated secondary gas mixture is introduced into pretreated raw material to and is made its mixing, cavitation process is carried out to gained mixture, liquids and gases product is detached, product oil is subsequently isolated out.The novelty of the present invention is using the gaseous hydrocarbon of the comparable activation energy of molecular dissociation energy with the key component with heavy hydrocarbon feeds as secondary gas mixture；When heavy hydrocarbon feeds and secondary gas mixture are in liquid, pre-processed with the pressure of the saturated vapor pressure more than secondary gas mixture.Technical result is, by the ingredient and its structure that change product oil, the physicochemical property of product oil is improved, the density, viscosity and initial boiling point of product oil are especially reduction of, the treatment effeciency and effect for improving the light fraction yield in refining process, improving heavy hydrocarbon feeds.

Description

The method for handling heavy hydrocarbon feeds

Technical field

The present invention relates to oil refining, petrochemical industry and chemical industry and oil and energy industries, and in particular to the processing of heavy crude hydrocarbon Method, and can be used for preparing and handle mink cell focus, oil refining and petrochemical industry residue, and for producing hydrocarbon fuel, petrochemical industry Product and chemical products and other liquid hydrocarbon mediums transported for mink cell focus.

Background technology

Transport heavy crude oil hydrocarbon (heavy crude) practical problem be reduce its viscosity and density, and reduce boiling point and Improve the yield of the lighter products in refining process.Currently for mink cell focus transport for, it usually in being pumped to pipeline it It is preceding to be diluted with petroleum benzin fraction (naphtha), and the volume of diluent can reach the 15 to 20% of heavy oil volume.

If naphtha cannot be transported to terminal and carry out oily dilution, its viscosity is heated to decrease in conveying.

Can also by cavitation reactor in a pure form and there are in the case of auxiliary additive handle mink cell focus come Reduce the viscosity and density of mink cell focus.The volume of diluent can be eliminated or be substantially reduced to the technology, and exclude to heat or reduce pipe The temperature of road heating.

The method of known a kind of heavy oil processing comprising prepared by oil, the preparation of auxiliary additive, the mixing of component, mixes Close the cavitation process of object, wherein use [1] of the pentane as auxiliary additive.

The disadvantages of this method is due to the use of pentane as auxiliary additive, so process efficiency is low.In identical temperature strip Under part, pentane activation energy is several times higher than the activation energy of mink cell focus high molecular weight component.Due to the significant difference of activation energy, mixture The number of free radical of middle light components is far below the number of free radical of heavy component.The segment of petroleum high-molecular amount component does not connect It is reacted with them by the free radical of the light components of sufficient amount, therefore their own recombines.For this treatment technology, weight The reduction of the density and viscosity of matter oil is primarily not the destruction due to the high-molecular weight compounds of mink cell focus, but since it is with penta Caused by alkane dilutes.

It is Method for treatment of oil [2] closest to the method for the processing of heavy crude hydrocarbon proposed comprising prepared by oil, auxiliary Help the preparation of additive (admixture of gas), component mixing, their processing and liquids and gases productions in cavitation reactor Object detaches, wherein uses associated gas as auxiliary additive (admixture of gas).Using injection cavitation process for association day The oil processing of right gas.At the same time, include that associated natural gas adds under 0.6 to 0.8MPa pressure using the oil processing of associated gas The temperature of heat to 120 DEG C accelerates to the supersonic speed more than 400m/s when Laval nozzle expands, pressure be 1.6Mpa, Oil stream in the heterotypic channel that temperature is 80 to 90 DEG C accelerates and its injection in cavitation jet air and liquid mixer is held with being formed Product cavitation cave, wherein supersonic speed natural gas flow is supplied on the direction coaxial and same with oily flow direction, it is thus oily Air-flow is interacted and is mixed in the two-phase medium moved with local supersonic speed, to obtain gas concentration not less than handled 10% mixture of the quality of oil, the mixture obtained is oriented to along special-shaped inflation channel, in special-shaped inflation channel The speed of the mixture reduces and compacting fluctuation occurs when across sound barrier, completes natural gas in the oil molten wherein Solution has carried out passive cavitation to remove excessive natural gas for stabilized mixture and by separator to reuse Repetition cavitation process in device-homogenizer.

The use of the shortcomings that the method is its energy intensity height according to prototype, oil processing efficiency is low low with process efficiency.At this In the case of kind, oily high molecular weight component (fraction to boil in 350 to 550 DEG C of temperature ranges) and its segment are with relatively high Reactivity, and be easily accessible addition oxidation reaction [3].Associated gas mainly contains methane (70 to 96%), as most simple Gaseous paraffin hydrocarbon representative, with high chemical stability [4].Therefore, though in the presence of a catalyst, in reaction zone Oil gas workable mixtures also must be at least with 350 DEG C of temperature.The cavitation process of association gas mixture (according to prototype) exists Occur under the maximum pressure of 1.6MPa at a temperature of 80 to 90 DEG C.This means that heavy hydrocarbon feeds are in liquid, methane is in gas State and temperature are insufficient to allow its activation.

For intensified response effect, reactive component must have comparable activation energy, and correspondingly be formed by certainly By the donor and receptor with approximately equal quantity in base.In the instance of the prototype, it if not meeting these rules, can drop significantly Low process efficiency.

Invention content

The present invention provides a kind of methods of processing heavy hydrocarbon feeds, and compared with prototype, this method permission is as complete as possible, has Effect ground processing high viscosity and highdensity oil and oil product, improve product oil by changing its ingredient and structure with low cost Physicochemical property.

The purpose of the present invention is to provide a kind of process modification methods of heavy crude hydrocarbon processing, wherein by using it His secondary gas mixture and other conditions prepare raw material and secondary gas mixture, pass through and change processed heavy hydrocarbon feeds Ingredient, structure and high heavy hydrocarbon conversion ratio ensure the improvement of the physical and chemical parameter of processed heavy hydrocarbon feeds, especially：It is close Degree, viscosity, the reduction of initial boiling point and the raising of the light fraction yield in distillation process, to improve heavy hydrocarbon feeds processing Effect and its efficiency, to promote process energy consumption reduce.

The purpose handles the method for (preferably, mink cell focus) to realize by heavy crude hydrocarbon, and the method includes oil It prepares, prepares secondary gas mixture at a given pressure, the secondary gas mixture of preparation is introduced into raw material and be mixed, Mixture cavitation process detaches liquids and gases product with further product oil extraction according to the present invention, using with With the molecular dissociation of the key component of heavy crude hydrocarbon can comparable activation energy gaseous hydrocarbon as secondary gas mixture, and And initial heavy hydrocarbon feeds and the auxiliary gas in liquid are carried out under the pressure higher than the saturated vapour pressure of secondary gas mixture The preparation of body mixture.

Moreover, under some cases of the method for the heavy crude hydrocarbon processing (preferably, heavy oil) of requirement protection, institute The method of it is proposed the difference is that：

Mink cell focus residue (residual fuel oil, tar, carbocoal tar), greasy filth (pitch-resin-paraffin deposit are used in varing proportions Object, fuel oil, oil storage, paraffin etc.), used machine oil and lubricating oil, the fraction containing mink cell focus, mink cell focus, oil-heavy oil, oil-half Tar, the mixture of oil-tar is as heavy hydrocarbon feeds；

Use the high-temperature catalytic cracked gas of oil and gas as the raw material for secondary gas mixture.

In general, heavy crude hydrocarbon processing method claimed be noteworthy characterized by compared with prototype essence, It is necessary, to obtain new technical result.

As requirement protection invention result and obtain technical result, the technical result is by being changed to The ingredient of product oil, structure improve the physical and chemical parameter of product oil, in particular, reducing its density, viscosity, boiling point, improves distillation Light fraction yield in the process, and improve the effect and its efficiency of the processing of heavy crude hydrocarbon.

Using the molecular dissociation with the key component with heavy crude hydrocarbon can comparable activation energy gaseous hydrocarbon as auxiliary Admixture of gas is helped, the physical and chemical parameter of product oil can be improved, in particular, by increasing the light fraction yield in distillation process With reduction boiling point the improvement of ingredient and structure is realized since density and viscosity declines.Heavy hydrocarbon feeds and secondary gas mixture (auxiliary additive) is in liquid and has under the pressure higher than the saturated vapour pressure of secondary gas mixture and heavy original The preliminary preparation of the gaseous hydrocarbon of the comparable activation energy of molecular dissociation energy of the key component of petroleum hydrocarbon, provides in cavitation reactor The reactive component of high concentration.Mixture cavitation process as pre-prepared heavy hydrocarbon feeds and secondary gas mixture as a result, Since heavy hydrocarbon feeds and secondary gas mixture have the fact that comparable activation energy, provided in cavitation reactor necessary dense The donor-receptor free radical of degree.As under the conditions of selected the cavitation of the mixture of processed substance as a result, by locating The maximum concentration of donor-receptor bioactive molecule is the cardinal principle for the effect for improving required product yield in the mixture of reason. During mixture cavitation process, forms gasoline due to the destruction of the high-molecular compound of heavy crude hydrocarbon and light oil evaporates Point, as a result, cause the density and viscosity of processed oil product to reduce.The increase of gasoline and light oil fraction content causes to locate The boiling temperature for the hydrocarbon class composition managed declines the increase with the light fraction yield in distillation process.

It is all these to improve the physical and chemical parameter of processed heavy hydrocarbon feeds, and also improve at hydrocarbon class composition The effect and process efficiency of reason.

In the technology cycle of the technique for heavy hydrocarbon feeds processing proposed, compared with prototype, raw material and auxiliary gas The missing of the warm-up phase of body mixture leads to the effect and its efficiency of the reduction and hydrocarbon class composition processing of process energy intensity Raising.

Description of the drawings

The essence of the present invention is illustrated by graphic material, and Fig. 1 is the process flow chart of heavy hydrocarbon feeds processing, and Fig. 2 is to show The figure of the mink cell focus variable density of the percentage of the secondary gas mixture in raw material is introduced into before depending on cavitation process, and And Fig. 3 is the heavy oil viscosity change of the percentage for the secondary gas mixture being introduced into before depending on cavitation process in raw material The figure of change.

Specific implementation mode

The embodiment modification of the processing method of the heavy crude hydrocarbon proposed is illustrated by process flow chart (referring to Fig. 1), Wherein 1- raw materials, 2- secondary gas mixtures, raw material prepared by 3-, admixture of gas prepared by 4-, raw material 3 and auxiliary prepared by 5- Help the mixing of admixture of gas 4, the cavitation process of 6- mixtures, 7- Oil-gas Separations, 8- product oils.In figure 2 and figure 3, it specifies The following contents：(prototype) known to 1-, what 2- was proposed.

The method of claimed heavy crude hydrocarbon processing (preferably, mink cell focus) can use known standard in industry Equipment and device are realized.

The method of the heavy crude hydrocarbon processing (preferably, mink cell focus) proposed includes as follows：(referring to the figure in Fig. 1)： Raw material 1 and secondary gas mixture 2 are prepared at a particular pressure, they are compressed into full higher than secondary gas mixture thus With the pressure of vapour pressure.Then, the raw material of preparation 3 and secondary gas mixture 4 are for example mixed 5 in a mixer.Later, exist The cavitation process 6 of obtained mixture is carried out in cavitation machine.Then, for example, separation liquid is gentle in gs-oil separator Body product 7, further discharges product oil 8 and unreacted gas, and the unreacted gas returns to secondary gas mixture 2 Tank in.In this case, using the comparable activation energy of molecular dissociation energy with the key component with heavy crude hydrocarbon Gaseous hydrocarbon carries out original as secondary gas mixture 2 under the pressure more than the saturated vapour pressure of secondary gas mixture 2 The preparation of material 1,3 and the secondary gas mixture 2,4 in liquid.

The heavy hydrocarbon feeds processing method proposed is carried out by carrying out catalytic cracking in cavitation reactor as follows.It is first First, the preliminary preparation for carrying out heavy hydrocarbon feeds and the secondary gas mixture (additive) in liquid supplies them from storage tank To feed preparation unit, wherein raw material is compressed into specified pressure, and the value of the pressure is steamed higher than the saturation of secondary gas mixture Air pressure.

Using gaseous hydrocarbon as with auxiliary with the comparable activation energy of the molecular dissociation of the key component of heavy crude hydrocarbon energy Help admixture of gas.For example, if the pyrolytic cracking gaseous product of oil and carburet hydrogen is used to be pressed as secondary gas mixture Power is not lower than the saturated vapor pressure of propylene (the maximum component of mixture of saturated vapor pressure in all components)), at 25 DEG C For 1.132MPa.The viscosity and density of raw material are higher, and the secondary gas mixture of mixture must be included before cavitation process The percentage of (additive) is bigger.

When liquid of the viscosity no more than 5000cSt is supplied to its air inlet, fluid dynamics cavitation unit can be effective Ground works.Based on this limitation, for the feedstock processing that viscosity is 20000cSt, the auxiliary gas mixing for introducing 2 weight % is needed Object, and for the feedstock processing that viscosity is 120000cSt, need the secondary gas mixture for introducing 12 to 15 weight %.

After the preparation, raw material and secondary gas mixture (additive) group are merged into mixing, for example, by supplying them It is given in mixer, is stirred in a mixer with liquid.

After the component mixing of preparation, by the way that mixture is supplied to cavitation process unit, (such as fluid dynamics are empty Change reactor) to carry out cavitation process to the mixture, wherein it is former to carry out heavy there are secondary gas mixture The chemical reaction of petroleum hydrocarbon catalytic cracking.

The preparation of mixture and the pressure of cavitation process for carrying out heavy hydrocarbon feeds and auxiliary additive necessarily are greater than auxiliary gas The saturated vapor pressure of body mixture, i.e. gas should be at liquefaction.

As cavitation process as a result, heavy hydrocarbon feeds by catalytic cracking, wherein with key component with heavy crude hydrocarbon Molecular dissociation can the hydrocarbon gas mixture of comparable activation energy be used as auxiliary additive, and cavitation is for use as catalyst.

In the case where generating cavitation to component mixture, when the key energy to fracture of heavy hydrocarbon molecule and the auxiliary gas of hydrocarbon The activation energy of body mixture (additive) have similar value when, due to heavy hydrocarbon molecule and the free radical of auxiliary substance destruction and The number of free radical of formation will be identical as the suitably selection of quality coefficient.

It is reduction due to the average molecular weight of hydrocarbon mixture that the viscosity and density of heavy hydrocarbon feeds, which reduce, wherein gasoline and light The content of matter oil distillate increases after treatment.

After cavitation process, obtained liquefied mixture is supplied to separator, in the separator from processing procedure Fluid oil products (finished product) are detached in middle unreacted or the gas of formation.After the separation such as low boiling component-hydrogen, methane, ethane Portion gas can be re-used as secondary gas mixture preparation raw material.

As a result, foring the product oil with improved physical and chemical parameter, especially there is the density, viscosity, boiling point reduced With increased light fraction yield.

The effect of the present invention is tested on the cavitation machine Γ y Л -180 that capacity is up to 7001/h, and is handled in consideration It is evaluated in the case of the variation of front and back heavy hydrocarbon physical and chemical parameter (for example, viscosity, density, initial boiling point, light fraction content). The use of there is density at 20 DEG C is 0.976g/cm³, viscosity is the Pacific Rubiales companies of the parameter of 22500cSt Oil is used as heavy hydrocarbon feeds.Initial boiling point is 242 DEG C.

According to the quantity of hydrocarbon class composition and secondary gas mixture ratio, at the heavy hydrocarbon (mainly mink cell focus) that is proposed The use of reason method carries out validation verification.

Using the molecular dissociation with the key component with heavy crude hydrocarbon can comparable activation energy appropriate hydrocarbon gas as auxiliary Admixture of gas, especially propylene content is helped to be at least 65 volume %, and unsaturated hydrocarbons total amount is not less than the catalysis of 80 volume % The mixture of cracked gas.

A heavy oil processing is carried out with the pattern that flows through with following parameter：Initial temperature is 22-25 DEG C, and pressure is 1.6Mpa, and material performance is 4501/h.

By under 1.6MPa pressure mink cell focus and secondary gas mixture be supplied to the entrance of cavitation machine operating room, in cavitation They are pre-mixed in machine operating room.

In addition, the mixture in liquid is supplied in the workspace that cavitation process occurs, subsequently into receiving tank.

The amount of the product of formation is by raw material physical and chemical parameter (viscosity, density, fraction and group constituents) and auxiliary additive (boiling Point, the saturated vapor pressure under operation temperature, chemical bond degree of unsaturation), fluid dynamics oscillation intensity and liquid rest on processing The time (performance) in area determines.After the cycle for completing heavy oil sample processing, superpressure is discharged from system, and by oil product Degassing is until remaining dissolved gas content is less than 1 weight %.Crude oil and acquisition are measured after deaerating under standard conditions (20 DEG C) The viscosity and density of oily product are as handling result.

Presentation depends on the hundred of the secondary gas mixture being introduced into before cavitation process in heavy hydrocarbon feeds in the following table Divide ratio and the experimental result of the physical and chemical parameter variation of the mink cell focus of measurement.

Table

Mink cell focus physical and chemical parameter depending on the percentage for being introduced into the secondary gas mixture in raw material before cavitation process Variation

The test result provided in table also shows that in the accompanying drawings (referring to Fig. 2 and Fig. 3).

The data of presentation middle with reference to the accompanying drawings, it can be deduced that draw a conclusion.

When handling the mink cell focus of Pacific Rubiales companies, according to the method proposed treated oil density Reduction amount is 0.033-0.048g/cm³(average value 0.0405g/cm³), and be 0.008-0.015g/cm according to prototype³, (flat Mean value is 0.0115g/cm³).Therefore, the variation that the density of the method proposed reduces is 3.5 times in prototype.By being carried The method gone out treated heavy oil viscosity reduces 8 times or more, and treated that heavy oil viscosity reduces by prototype 1.6 times.

In order to compare heavy hydrocarbon feeds physical and chemical parameter before and after the processing and determine technique effect and efficiency, to before and after the processing The oil of Pacific Rubiales companies is fractionated.Shown in such as testing, the boiling point of crude oil is 242 DEG C, and light fraction yield is The boiling point of 55.5 volume %, the oil handled by prototype are 181 DEG C, and light fraction yield is 63%, by according to the side proposed It is 74.5 volume % that the oil of method processing, which has 127 DEG C of boiling point, light fraction yield,.

Industrial applicibility

The method for handling heavy hydrocarbon feeds proposed can be used for multi-component liquid processing comprising oil and oil production The modification of product especially reduces their viscosity and density to improve their consumption property.The present invention is industrially that can answer , and can be implemented by the method industrially realized by using any means known and equipment.

The test carried out shows to be handled so that density averagely reduces 0.0405g/ according to the heavy oil of the method proposed cm³, 8 times of viscosity reduction or more, 115 DEG C of boiling point reduction, light fraction yield increases by 19 volume %.

The possibility of embodiment of the present invention is explained above and is realizing whole inventions described in the present invention program Above-mentioned technical result can be realized when feature.It makes it possible to generate using essential whole features of claimed invention For the technology of heavy hydrocarbon processing, there is Consumer Characteristics more higher than known technology, and lower process energy density and height Process efficiency.

The method of the heavy hydrocarbon processing proposed can be used for reducing viscosity and density by petroleum pipeline before conveying, and The light fraction yield during oil distillation can also be improved.

Information resources

1. priority date disclosed in 31 days January in 2012 is the United States Patent (USP) US8105480B2M Π K C on March 6th, 2007 10G 9/00。

The Russ P RU 2436834, M that 2. publication date is on December 20th, 2011, priority date is on March 15th, 2010 Π K C10G 015/00, C10G 04732 (prototype).

3. petroleum and natural gas is chemical.V.A. Corvidae husband and A.E. Drabkins in Prologis library.-M：Chemistry, nineteen ninety-five, 294 Page.

It is strange that 4.E.V. likes meter Duo Wei.Petroleum and natural gas processing technology.Part 2.Crude oil pyrolysis is handled with hydrocarbon gas.M.： Chemistry, 1980, page 52.

5. petrochemistry expert's Guide Book.S.K. Ao Geluode Nicos husband.1st, L.：Chemistry, 1978, page 67.

Claims

1. method of the one kind for handling heavy hydrocarbon feeds, especially mink cell focus, including：Raw material and auxiliary are prepared at a given pressure The secondary gas mixture of preparation is introduced into the raw material prepared and is mixed, carried out to gained mixture by admixture of gas Cavitation process detaches liquids and gases product, then recycles product oil, which is characterized in that use has and heavy crude hydrocarbon The molecular dissociation of key component can comparable activation energy gaseous hydrocarbon as secondary gas mixture, also, than auxiliary gas The preparation of heavy hydrocarbon feeds and the secondary gas mixture in liquid is carried out under the high pressure of the saturated vapor pressure of mixture.

2. the method according to claim 1 for handling heavy hydrocarbon feeds, especially mink cell focus, which is characterized in that with not In proportion use mink cell focus residue (residual fuel oil, tar, carbocoal tar), greasy filth (pitch-resin-paraffin deposit object, fuel oil, Oil storage, paraffin etc.), used machine oil and lubricating oil, the fraction containing mink cell focus, mink cell focus, oil-heavy oil, oil-carbocoal tar, oil- The mixture of tar is as heavy hydrocarbon feeds.

3. the method according to claim 1 for handling heavy hydrocarbon feeds, especially mink cell focus, which is characterized in that use Natural gas or associated gas or propane-butane mixture, or the high-temperature catalytic cracking gas of oil and gas are used as assisting gas mixed Close the raw material of object.