CN106635161A - Method for preparing coal-based heavy liquid paraffin from coal indirect liquefaction oil product and coal-based heavy liquid paraffin prepared through method - Google Patents
Method for preparing coal-based heavy liquid paraffin from coal indirect liquefaction oil product and coal-based heavy liquid paraffin prepared through method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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Abstract
The invention discloses a method for preparing coal-based heavy liquid paraffin from a coal indirect liquefaction oil product and the coal-based heavy liquid paraffin prepared through the method. The method for preparing the coal-based heavy liquid paraffin from the coal indirect liquefaction oil product comprises the steps of hydrofining, fractionation and dewaxing. The heavy liquid paraffin obtained through the method has the properties of being high in n-alkane content, free of arene, sulfur and nitrogen and low in preparation cost and is a high-quality chemical raw material. According to the method, the range of raw materials and preparation methods of the heavy liquid paraffin applied to the industries such as nylon, cosmetics, pharmacy and the like is widened.
Description
Technical field
The invention belongs to coal chemical technology, is related to the utilization of indirect coal liquefaction oil product, and in particular to a kind of coal is indirect
The liquefaction oil product method for preparing coal base Paraffin liquid heavy and its coal base Paraffin liquid heavy for preparing.
Background technology
The main fuel that oil is used as our times, is faced with increasingly exhausted crisis.From in terms of world wide,
The reserves of coal exceed well over petroleum reserves.By the way that coal is converted into liquid fuel with the technique of high-efficiency cleaning, it will effectively alleviate
The pressure of oil supply.Therefore, the technology of indirect coal liquefaction technology-F- T synthesis production liquid fuel is paid close attention to increasingly.
Fischer-Tropsch synthetic includes light ends oil, heavy distillate, heavy wax etc..Fischer-Tropsch synthetic is mainly linear paraffinic hydrocarbons and alkene
Hydrocarbon, without sulphur, nitrogen-free, free from admixture.Fischer-Tropsch synthetic after treatment, can produce liquid fuel and chemicals.
Atoleine key component is n-alkane, is divided because the distribution of the components such as C10, C11, C12, C13 and C14 is different
For light wax (C10~C13) and weight wax (C14 or more).N-alkane (commonly referred to atoleine) is a kind of colourless, tasteless
Thick liquid, is a kind of important industrial chemicals, and a series of chemical products, such as chlorinated paraffin, farm chemical emulgent, fat can be obtained
Fat alcohol, synthetic detergent, plastic plasticizer, fertilizer additive and cosmetics, protein concentrate etc..Wherein heavy-fluid wax is mainly used in
Production chlorinated paraffin, T50 plasticizer, Premium detergents, fertilizer additive, leather oiling agent, fire retardant and lube oil additive
Deng.
At present, domestic Paraffin liquid heavy typically adopts boat coal or diesel oil distillate as raw material, by urea dewaxing technology
Produce.Petroleum chemical industry is affected by raw material, and the possibility for increasing liquid wax device newly is less.In F- T synthesis hydrofinishing product
Normal paraffin content about 85%, is production Paraffin liquid heavy far above the normal paraffin content of petroleum based oils about 50%
Good raw material.
The application for a patent for invention of Application No. 201510073222.0 discloses one kind and prepares liquid by Fischer-Tropsch synthetic
The method of paraffin, paraffin precursor and lube base oil precursor, its production atoleine cut do not distinguish lightweight, heavy and
Other products, and product is not refined through dewaxing, it is impossible to products perfection is realized, economic rationality is poor.
The content of the invention
The present invention overcomes the deficiencies in the prior art, technical problem to be solved to be to provide a kind of indirect coal liquefaction oil product
The method for preparing coal base Paraffin liquid heavy.
In order to solve above technical problem, the present invention provides a kind of indirect coal liquefaction oil product and prepares coal base heavy liquid stone
The method of wax and its coal base Paraffin liquid heavy for preparing, comprise the following steps:
(1) indirect coal liquefaction oil product and hydrogen are mixed into hydrofining reactor contacting with hydrogenation catalyst is carried out
Hydrofining reaction, obtains hydrorefined oil product;The hydrogenation deoxidation reaction of the hydrofining reaction including oxygenatedchemicals,
Hydrogenation saturated reaction and trace meter adsorbing and removing of unsaturated hydrocarbons etc.;
(2) the hydrorefined oil product is fractionated into fractionating system, obtains the cut of 260~320 DEG C of boiling ranges, that is, weighed
Matter atoleine precursor;Through the fractionation can isolate naphtha, liquid paraffin,light precursor, Paraffin liquid heavy precursor,
Refined heavy diesel fuel, refined tail oil and diesel product;
(3) the Paraffin liquid heavy precursor is dewaxed, obtains coal base Paraffin liquid heavy;
The Paraffin liquid heavy refers to C14~C18 n-alkanes.
In said method, the weight/mass percentage composition of the n-alkane in the Paraffin liquid heavy precursor is 75~92%.
In said method, hydrofining reactor described in step (1) is fixed bed reactors;
The fixed bed reactors are preferably an independent fixed bed reactors.
In any of the above-described described method, hydrogenation catalyst described in step (1) is metal load type catalyst, and carrier is
Unformed aluminum oxide, metal component is at least one in the group selected from Mo, Co, Ni and W composition;
The catalyst appearance can be the shapes such as seven apertures in the human head ball, four impellers, bunge bedstraw herb, and 1.0~5.5mm of particle diameter is pressed
Broken intensity is not less than 5N/ grains, it is preferable that the catalyst be bunge bedstraw herb shape, 1.0~1.5mm of particle diameter, crushing strength is not
Less than 10N/ grains.Material to better control over beds is distributed and pressure drop, plays the reactivity worth of catalyst, and prolongation is urged
The service life of agent, catalyst in reactor is divided into multilayer filling.
In any of the above-described described method, hydrorefined reaction condition is described in step (1):Hydrogen to oil volume ratio is
100~800, reaction temperature is 260~420 DEG C, and reaction pressure is 3.0~10.0MPa, and volume space velocity is 1.0~5.0h-1;
The hydrorefined reaction condition is preferably:Hydrogen to oil volume ratio is 400~600, and reaction temperature is 270~370
DEG C, reaction pressure is 6.0~9.0MPa, and volume space velocity is 1.0~3.0h-1;
The hydrorefined reaction condition is more preferably:Hydrogen to oil volume ratio is 500, and reaction temperature is 275~365 DEG C,
Reaction pressure is 8.0MPa, and volume space velocity is 1.0~2.4h-1;
Also included the step of heating to the indirect coal liquefaction oil product before step (1) is carried out, heating-up temperature is 250
~400 DEG C, preferably 270~365 DEG C, more preferably 270~325 DEG C.
In any of the above-described described method, it is fractionated described in step (2) as normal pressure fractionation:The theoretical cam curve of atmospheric tower is
50~60, tower top temperature is 140~170 DEG C, and column bottom temperature is 320~350 DEG C, and pressure is 0.15~0.25MPa;Atmospheric tower sets
There are 2 and above side line, wherein the boiling range of normal line component is 160~260 DEG C, the cut rich in C10~C13;Normal two wires group
Fractionation journey is 260~320 DEG C, wherein rich in the Paraffin liquid heavy precursor.
In any of the above-described described method, dewaxing described in step (3) is urea dewaxing.
In said method, the dewaxing process is as follows:
1) complex reaction:Be there is into complex reaction in the Paraffin liquid heavy precursor and complexing agent mixing and generate solid complexing
Thing is precipitated, wherein, complexing agent:Oil product (volume ratio)=(6~15):1, the temperature of complex reaction is 20~35 DEG C, the reaction time 1
~5h;
The complexing agent is the isopropanol and urea aqueous solution, wherein urea:Isopropanol:Water (volume ratio)=(35~45):(35
~45):(15~25);
2) complex compound is separated with dewaxed oil:By step 1) sedimentation separation is carried out under the mixture normal temperature that obtains, during sedimentation
Between be 0.5h~1h, obtain lower floor's solid complex;The dewaxed oil is that the Paraffin liquid heavy precursor is removed by the network
The remainder of the n-alkane of mixture complexing;
3) washing of complex compound:By step 2) solid complex adopt 200# solvent oil wash, washing oil volume ratio be (1
~3):1, washing times are 1~3 time;
4) complex compound decomposes:By step 3) complex compound and water after washing is mixed and heated to temperature for 55~70 DEG C, makes
Obtain complex compound to decompose, obtain the Paraffin liquid heavy;
Preferably, step 1) described in complexing agent:Oil product (volume ratio)=(10~15):1, the temperature 25 of complex reaction~
33 DEG C, 2~5h of reaction time;Urea in complexing agent:Isopropanol:Water (volume ratio)=(38~42):(40~44):(15~
20);It is highly preferred that step 1) described in complexing agent:Oil product (volume ratio)=13:1;Urea in complexing agent:Isopropanol:Water (body
Product ratio)=40:42:18;
Preferably, step 4) in complex compound after washing mix with water and be preferably heated to 60~65 DEG C of temperature.
In any of the above-described described method, the indirect coal liquefaction oil product can be that the full cut of oil from Fischer-Tropsch synthesis is produced
The mixture of some cuts in the full cut of thing or oil from Fischer-Tropsch synthesis.
In order to solve above technical problem, the present invention also provides the coal base prepared according to any of the above-described described method
Paraffin liquid heavy;
The Paraffin liquid heavy refers to C14~C18 n-alkanes.
In order to solve above technical problem, the present invention also provides indirect coal liquefaction oil product and is preparing coal base heavy liquid stone
Application in wax;
The Paraffin liquid heavy refers to C14~C18 n-alkanes.
In above-mentioned application, the indirect coal liquefaction oil product can be that the full cut product of oil from Fischer-Tropsch synthesis or Fischer-Tropsch are closed
The mixture of some cuts into the full cut of oil product.
The indirect coal liquefaction oil product that the present invention is provided prepares coal base Paraffin liquid heavy method and at least has the advantage that:
The method is prepared into performance excellent using indirect coal liquefaction oil product as raw material by hydrofinishing, fractionation and dewaxing
Good Paraffin liquid heavy, the atoleine have normal paraffin content it is high, without aromatic hydrocarbons, without unique property such as sulphur, nitrogen-free simultaneously
It is a kind of industrial chemicals of high-quality and preparation cost is low.
The method of the present invention widened the raw material of the Paraffin liquid heavy for being applied to the industries such as nylon, cosmetics, pharmacy and
Preparation method.
Specific embodiment
Experimental technique used in following embodiments if no special instructions, is conventional method.
Material used, reagent etc. in following embodiments, if no special instructions, commercially obtain.
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for restriction the scope of the present invention.
Oil from Fischer-Tropsch synthesis is Inner Mongolia Yitai Group Co., Ltd.'s product, wherein 30~200 DEG C of light hydrocarbon boiling range, heavy
150~700 DEG C of hydrocarbon boiling range, sulfur content is less than 5mg/kg.
The FZC-33 products that fixed bed hydrogenation catalyst is developed for Fushun Petrochemical Research Institute, bunge bedstraw herb shape, particle
1.0~1.5mm of diameter, crushing strength is not less than 10N/ grains.Material to better control over beds is distributed and pressure drop, sends out
The reactivity worth of catalyst is waved, extends the service life of catalyst, catalyst in reactor is divided into three layers of filling.
Embodiment 1, indirect coal liquefaction oil product prepare coal base Paraffin liquid heavy
This method is substantially carried out hydrofinishing, fractionation with indirect coal liquefaction oil product (i.e. oil from Fischer-Tropsch synthesis) as raw material
Coal base Paraffin liquid heavy is prepared with three steps of dewaxing, it is specific as follows:
1st, hydrogenation technique flow process:The loading catalyst inside fixed bed reactors, in order to better control over exothermic heat of reaction, will
Gross mass is by volume from top to bottom 1 for the hydrogenation catalyst of 58t:1.2:1.7 ratio, points three layers fill in volume and are
212m3Internal diameter is in the fixed bed reactors of 4.4m;Indirect coal liquefaction oil product and fresh hydrogen are heated into 270~325 DEG C
Afterwards, enter from the top of fixed bed reactors;Hydrogen, oil product material and catalyst are sufficiently mixed inside fixed bed to carry out adding
Hydrogen reacts, and hydrogen to oil volume ratio is 500, and reaction temperature is controlled at 275~365 DEG C, and reaction pressure is 8MPa, and volume space velocity is 1.0
~2.4h-1;Reactant after catalytic hydrogenation is obtained into oil product part, as hydrorefined oil Jing after gs-oil separator separation
Product, by hydrorefined oil product follow-up fractionating system is entered.
Paraffin liquid heavy in raw material oil from Fischer-Tropsch synthesis and hydrorefined oil product is detected with SH/T0416-2014 methods
And the content of the n-alkane in Paraffin liquid heavy, as a result as shown in table 1.
2nd, fractionating system:The hydrorefined oil product that step 1 is obtained is passed through into atmospheric tower carries out normal pressure fractionation, atmospheric tower
Theoretical cam curve be 50~60, tower top temperature be 140~170 DEG C, column bottom temperature be 320~350 DEG C, pressure be 0.15~
0.25MPa;Atmospheric tower is provided with 2 and above side line, wherein normal two wires extracts the cut that boiling range is 260~320 DEG C out, to the cut
Gas chromatographic detection is carried out, as a result shows that it is rich in C14~C18 alkane, the cut is Paraffin liquid heavy precursor.
With the method in step 1 detect normal two wires extract in cut (i.e. Paraffin liquid heavy precursor) Paraffin liquid heavy out with
And the normal paraffin content in Paraffin liquid heavy, as a result as shown in table 1.
3rd, urea dewaxing refers to that utilizing n-alkane and urea in oil to react in alcohol solution generates solid complex, then
It is separated from oil, then at relatively high temperatures decomposes complex compound, obtain n-alkane and urea, wherein urea cycle
Use.It is specific as follows:
1) complex reaction:Solid network generated and complex reaction in the Paraffin liquid heavy precursor that step 2 is obtained and urea there is
Compound is precipitated, wherein, complexing agent:Oil product (volume ratio)=13:1, the temperature of complex reaction is 25~33 DEG C, the reaction time 2~
5h, complexing agent be the isopropanol and urea aqueous solution, urea:Isopropanol:Water (volume ratio)=40:42:18;
2) complex compound is separated with dewaxed oil:According to the difference in specific gravity of complex compound and dewaxing liquid, by step 1) mixing that obtains
Sedimentation separation is carried out under thing normal temperature, the sedimentation time is 0.5h~1h, obtains lower floor's solid complex;
3) washing of complex compound:By step 2) the solid complex 200# solvent oil wash that obtains, washing oil ratio (volume
Than) it is (1~3):1, washing times are 2 times, and the dewaxed oil on complex compound surface is washed;
4) complex compound decomposes:By step 3) complex compound and water after washing is mixed and heated to temperature for 60~65 DEG C, makes
Obtain complex compound to decompose, finally give Paraffin liquid heavy and urea.
With in Paraffin liquid heavy in the method detection coal base Paraffin liquid heavy in step 1 and Paraffin liquid heavy
Normal paraffin content, as a result as shown in table 1.
The composition detection of each work-in-process of table 1
Embodiment 2, indirect coal liquefaction oil product prepare coal base Paraffin liquid heavy
The raw material that raw material is used with embodiment 1 is identical, is substantially carried out hydrofinishing, fractionation and three steps that dewax prepare coal
Base Paraffin liquid heavy, it is specific as follows:
1st, hydrogenation technique flow process:The filling of fixed bed reactors and catalyst is same as Example 1;By indirect coal liquefaction
After oil product and fresh hydrogen are heated to 270~325 DEG C, enter from the top of fixed bed reactors;By hydrogen, oil product material and urge
Agent is sufficiently mixed inside fixed bed carries out hydrogenation reaction, and hydrogen to oil volume ratio is 300, and reaction temperature is controlled 275~365
DEG C, reaction pressure is 6MPa, and volume space velocity is 1.0~2.4h-1;By the reactant after catalytic hydrogenation Jing after gs-oil separator separation
Oil product part is obtained, hydrorefined oil product is entered follow-up fractionating system by as hydrorefined oil product.
Paraffin liquid heavy in raw material oil from Fischer-Tropsch synthesis and hydrorefined oil product is detected with SH/T0416-2014 methods
And the content of the n-alkane in Paraffin liquid heavy, as a result as shown in table 2.
2nd, fractionating system:The hydrorefined oil product that step 1 is obtained is passed through into atmospheric tower carries out normal pressure fractionation, atmospheric tower
Theoretical cam curve be 50~60, tower top temperature be 140~170 DEG C, column bottom temperature be 320~350 DEG C, pressure be 0.15~
0.25MPa;Atmospheric tower is provided with 2 and above side line, wherein normal two wires extracts the cut that boiling range is 260~320 DEG C out, to the cut
Gas chromatographic detection is carried out, as a result shows that it is rich in C14~C18 alkane, the cut is Paraffin liquid heavy precursor.
With the method in step 1 detect normal two wires extract in cut (i.e. Paraffin liquid heavy precursor) Paraffin liquid heavy out with
And the normal paraffin content in Paraffin liquid heavy, as a result as shown in table 2.
3rd, urea dewaxing.It is specific as follows:
1) complex reaction:Solid network generated and complex reaction in the Paraffin liquid heavy precursor that step 2 is obtained and urea there is
Compound is precipitated, wherein, complexing agent:Oil product (volume ratio)=14:1, the temperature of complex reaction is 25~33 DEG C, the reaction time 2~
5h, complexing agent be the isopropanol and urea aqueous solution, urea:Isopropanol:Water (volume ratio)=42:40:18;
2) complex compound is separated with dewaxed oil:According to the difference in specific gravity of complex compound and dewaxing liquid, by step 1) mixing that obtains
Sedimentation separation is carried out under thing normal temperature, the sedimentation time is 0.5h~1h, obtains lower floor's solid complex;
3) washing of complex compound:By step 2) the solid complex 200# solvent oil wash that obtains, washing oil ratio (volume
Than) it is (1~3):1, washing times are 2 times, and the dewaxed oil on complex compound surface is washed;
4) complex compound decomposes:By step 3) complex compound and water after washing is mixed and heated to temperature for 60~65 DEG C, makes
Obtain complex compound to decompose, finally give Paraffin liquid heavy and urea.
With in Paraffin liquid heavy in the method detection coal base Paraffin liquid heavy in step 1 and Paraffin liquid heavy
Normal paraffin content, as a result as shown in table 2.
The composition detection of each work-in-process of table 2
Embodiment 3, indirect coal liquefaction oil product prepare coal base Paraffin liquid heavy
The raw material that raw material is used with embodiment 1 is identical, is substantially carried out hydrofinishing, fractionation and three steps that dewax prepare coal
Base Paraffin liquid heavy, it is specific as follows:
1st, hydrogenation technique flow process:The filling of fixed bed reactors and catalyst is same as Example 1;By indirect coal liquefaction
After oil product and fresh hydrogen are heated to 370~400 DEG C, enter from the top of fixed bed reactors;By hydrogen, oil product material and urge
Agent is sufficiently mixed inside fixed bed carries out hydrogenation reaction, and hydrogen to oil volume ratio is 700, and reaction temperature is controlled 380~410
DEG C, reaction pressure is 9MPa, and volume space velocity is 1.0~2.4h-1;By the reactant after catalytic hydrogenation Jing after gs-oil separator separation
Oil product part is obtained, hydrorefined oil product is entered follow-up fractionating system by as hydrorefined oil product.
Paraffin liquid heavy in raw material oil from Fischer-Tropsch synthesis and hydrorefined oil product is detected with SH/T0416-2014 methods
And the content of the n-alkane in Paraffin liquid heavy, as a result as shown in table 3.
2nd, fractionating system:The hydrorefined oil product that step 1 is obtained is passed through into atmospheric tower carries out normal pressure fractionation, atmospheric tower
Theoretical cam curve be 50~60, tower top temperature be 140~170 DEG C, column bottom temperature be 320~350 DEG C, pressure be 0.15~
0.25MPa;Atmospheric tower is provided with 2 and above side line, wherein normal two wires extracts the cut that boiling range is 260~320 DEG C out, to the cut
Gas chromatographic detection is carried out, as a result shows that it is rich in C14~C18 alkane, the cut is Paraffin liquid heavy precursor.
With the method in step 1 detect normal two wires extract in cut (i.e. Paraffin liquid heavy precursor) Paraffin liquid heavy out with
And the normal paraffin content in Paraffin liquid heavy, as a result as shown in table 3.
3rd, urea dewaxing.It is specific as follows:
1) complex reaction:Solid network generated and complex reaction in the Paraffin liquid heavy precursor that step 2 is obtained and urea there is
Compound is precipitated, wherein, complexing agent:Oil product (volume ratio)=12:1, the temperature of complex reaction is 25~33 DEG C, the reaction time 2~
5h, complexing agent be the isopropanol and urea aqueous solution, urea:Isopropanol:Water (volume ratio)=38:40:18;
2) complex compound is separated with dewaxed oil:According to the difference in specific gravity of complex compound and dewaxing liquid, by step 1) mixing that obtains
Sedimentation separation is carried out under thing normal temperature, the sedimentation time is 0.5h~1h, obtains lower floor's solid complex;
3) washing of complex compound:By step 2) the solid complex 200# solvent oil wash that obtains, washing oil ratio (volume
Than) it is (1~3):1, washing times are 2 times, and the dewaxed oil on complex compound surface is washed;
4) complex compound decomposes:By step 3) complex compound and water after washing is mixed and heated to temperature for 60~65 DEG C, makes
Obtain complex compound to decompose, finally give Paraffin liquid heavy and urea.
With in Paraffin liquid heavy in the method detection coal base Paraffin liquid heavy in step 1 and Paraffin liquid heavy
Normal paraffin content, as a result as shown in table 3.
The composition detection of each work-in-process of table 3
Claims (10)
1. the method that indirect coal liquefaction oil product prepares coal base Paraffin liquid heavy, comprises the following steps:
(1) indirect coal liquefaction oil product and hydrogen are mixed into hydrofining reactor contact with hydrogenation catalyst and be hydrogenated with
Refining reaction, obtains hydrorefined oil product;
(2) the hydrorefined oil product is fractionated into fractionating system, obtains the cut of 260~320 DEG C of boiling ranges, i.e. heavy liquid
Body paraffin precursor;
(3) the Paraffin liquid heavy precursor is dewaxed, obtains coal base Paraffin liquid heavy.
2. method according to claim 1, it is characterised in that:The matter of the n-alkane in the Paraffin liquid heavy precursor
Amount percentage composition is 75~92%.
3. method according to claim 1, it is characterised in that:Hydrofining reactor described in step (1) is fixed bed
Reactor.
4. the method according to any one of claim 1-3, it is characterised in that:Hydrogenation catalyst described in step (1) is gold
Category loaded catalyst, carrier be unformed aluminum oxide, metal component be selected from Mo, Co, Ni and W composition group at least
It is a kind of.
5. the method according to any one of claim 1-4, it is characterised in that:Hydrorefined reaction described in step (1)
Condition is:Hydrogen to oil volume ratio be 100~800, reaction temperature be 260~420 DEG C, reaction pressure be 3.0~10.0MPa, volume
Air speed is 1.0~5.0h-1。
6. the method according to any one of claim 1-5, it is characterised in that:It is fractionated described in step (2) as normal pressure fractionation:
The theoretical cam curve of atmospheric tower is 50~60, and tower top temperature is 140~170 DEG C, and column bottom temperature is 320~350 DEG C, and pressure is
0.15~0.25MPa;Atmospheric tower is provided with 2 and above side line, and normal two wires component boiling range is 260~320 DEG C, wherein rich in described
Paraffin liquid heavy precursor.
7. the method according to any one of claim 1-6, it is characterised in that:Dewaxing described in step (3) is urea dewaxing.
8. method according to claim 7, it is characterised in that:The dewaxing process is as follows:
1) complex reaction:The Paraffin liquid heavy precursor and complexing agent mixing into complex reaction generation solid complex occur to sink
Form sediment, wherein, complexing agent:Oil product (volume ratio)=(6~15):1, the temperature of complex reaction is 20~35 DEG C;
The complexing agent is the isopropanol and urea aqueous solution, wherein urea:Isopropanol:Water (volume ratio)=(35~45):(35~
45):(15~25);
2) complex compound is separated with dewaxed oil:By step 1) sedimentation separation is carried out under the mixture normal temperature that obtains, obtain lower floor and consolidate
Body complex compound;The dewaxed oil is the residue that the Paraffin liquid heavy precursor removes the n-alkane being complexed by the complexing agent
Part;
3) washing of complex compound:By step 2) solid complex adopt 200# solvent oil wash, washing oil volume ratio be (1~3):
1;
4) complex compound decomposes:By step 3) complex compound and water after washing is mixed and heated to temperature for 55~70 DEG C so that network
Compound decomposes, and obtains the Paraffin liquid heavy.
9. the coal base Paraffin liquid heavy that the arbitrary described method of claim 1-8 is prepared.
10. application of the indirect coal liquefaction oil product in coal base Paraffin liquid heavy is prepared.
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CN104611059A (en) * | 2015-02-12 | 2015-05-13 | 武汉炼化工程设计有限责任公司 | Method for preparing liquid paraffin, paraffin precursor and lubricant base oil precursor from Fischer-Tropsch synthesis products |
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