CN1297635C - Process for preparing naphtha materials special for ethylene production device by using Fisher-Tropsch synthetic products - Google Patents
Process for preparing naphtha materials special for ethylene production device by using Fisher-Tropsch synthetic products Download PDFInfo
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Abstract
The present invention relates to a method for producing special naphtha materials for an ethylene device from Fisher-Tropsch synthetic products. The producing method comprises that all or lighter cut fractions of Fischer-Tropsch synthesized products are hydrotreated, and part of or all of the hydrotreated Fischer-Tropsch synthesized products and / or heavier cut fractions of the Fischer-Tropsch synthesized products which are not hydrotreated are hydrocracked; the hydrotreated products and hydrocracked products or the mixture of the hydrotreated products and the hydrocracked products are fractionated, gas, lightweight cut fractions, intermediate cut fractions and heavy cut fractions can be obtained, wherein the heavy cut fractions are returned to a hydroisomerizing cracking reactor as circulating oil. The lightweight cut fractions are the special naphtha materials for an ethylene device. The present invention has the material index that the paraffinics content is larger than 70 wt%, the normal alkane content is larger than 40 wt%, the sulfur content is less than 0.05 ppm, and the final boiling point (FBP) is lower than 200.
Description
Technical field
The present invention relates to a kind of the synthetic hydrocarbon that is produced of Fischer-Tropsch and the method for derivative processing treatment thereof are referred more particularly to hydrotreatment, hydrocracking and fractionated method and handle Fischer-Tropsch synthetic, to produce the method for ethylene unit naphtha materials special.
Background technology
Along with based on the increase of the liquid fuel demand of oil and the minimizing of petroleum resources usable reserves, the method for being produced the available liquid fuel by solid fuels such as coals more and more is subject to people's attention.
Solid-fuelled liquefaction has two kinds of different technological lines, and a kind of is direct liquefaction, and a kind of is indirect liquefaction.Direct liquefaction is under High Temperature High Pressure, solid fuels such as coal is converted into the technology of liquefaction oil under the effect of solvent and catalyzer.Direct liquefaction operational condition harshness is strong to the dependency of raw material.
Indirect liquefaction is that the Fischer-Tropsch of common indication is synthetic, is under the condition that iron-based, cobalt-based or iron cobalt-base catalyst exist, and will comprise carbon monoxide (CO) and hydrogen (H by what solid fuels such as coal produced
2) synthetic gas, under certain temperature and pressure, the technology of directional catalyzing synthin fuel and industrial chemicals.Indirect liquefaction is strong to the suitability of raw material, and range of product is many, institute's produce oil product quality height.
Fischer-Tropsch synthetic main products is C
5Above, based on the hydro carbons of normal paraffin, wherein also contain part alkene and hydrocarbon oxide etc.These products can be used as intermediates and produce available products such as petrochemical materials or transport fuel through reprocessing.
Fischer-Tropsch synthetic is after processing treatment, and middle runnings can be in order to produce diesel oil and aviation kerosene, and heavy ends can be in order to produce paraffin or lube base wet goods.And wherein lighter naphtha fraction then can be produced the special raw material of fine steam pyrolysis system ethylene unit.
In petroleum refining industry, petroleum naphtha can also can be used as the light aromatic hydrocarbons of raw material production or the stop bracket gasoline of catalytic reforming directly as gasoline component, or is used as the raw material of steam pyrolysis system ethylene unit, produces light olefins such as ethene.And the petroleum naphtha of being produced by Fischer-Tropsch synthetic is mainly by alkane, particularly normal paraffin is formed, almost aromatic free and naphthenic hydrocarbon, octane value and virtue are dived all very low, no matter be directly as gasoline component, still light aromatic hydrocarbons of raw material production or the stop bracket gasoline as catalytic reforming all is not that ideal utilizes approach.
Ethene is one of important symbol of weighing a country petrochemical industry developmental level.At present China's ethylene requirements increases fast, and being that the synthetic resins such as polyethylene, polypropylene, polystyrene of raw material are over half with ethene still relies on import.Steam pyrolysis system ethene is the main source of ethene, uses steam pyrolysis system ethylene unit, when producing ethene, can obtain the basic material of petrochemical compleies such as propylene, butylene.In China, home-made crude oil is heavier, and the petroleum naphtha or the solar oil raw material that can be used for producing ethene are less.Simultaneously, petroleum naphtha in the petroleum fractions and solar oil are the main raw materials of producing motor spirit, if petroleum naphtha in the petroleum fractions and solar oil are used as the raw material of producing ethene, the phenomenon that certainly will cause ethylene unit and oil fuel device to contend over raw materials in a large number.If make ethylene raw with petroleum fractionss such as heavier intermediate base, paraffinic bases, the productive rate of olefin products such as not only installation cost height, and ethene also can descend.This situation impels the production of China's ethylene unit need walk the diversified road of raw material.
Summary of the invention
Purpose of the present invention is exactly for a kind of method of producing the ethylene unit naphtha materials special with Fischer-Tropsch synthetic is provided, with the naphtha fraction that utilizes the Fischer-Tropsch synthesis oil course of processing to produce more effectively and reasonably.
Purpose of the present invention can be achieved through the following technical solutions: a kind of method of producing the ethylene unit naphtha materials special with Fischer-Tropsch synthetic is characterized in that this method may further comprise the steps:
(1) Fischer-Tropsch synthetic is whole or lighter part cut carries out hydrotreatment, and the condition of hydrotreatment is: 260～400 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0～18MPa, volume space velocity 0.1～15h during liquid
-1, hydrogen to oil volume ratio 200～1600;
(2) will partly or entirely and/or without the heavier part cut of the Fischer-Tropsch synthetic of hydrotreatment carry out hydrocracking through the Fischer-Tropsch synthetic of hydrotreatment, the condition of hydrocracking is: 300～460 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0～18MPa, volume space velocity 0.1～10h during liquid
-1, hydrogen to oil volume ratio 500～2400;
(3) product of fractionation hydrotreatment and hydrocracking gained or both mixtures, can obtain gas, light ends, middle runnings and heavy ends, wherein heavy ends turns back to hydrocracking reactor as turning oil, and light ends is the ethylene unit naphtha materials special.
The index of described ethylene unit naphtha materials special is: alkane content is greater than 70wt%, and normal paraffin is greater than 40wt%, and sulphur content is less than 0.05PPm, and full boiling point (FBP) is below 200.
Described Fischer-Tropsch synthetic also comprises from Fischer-Tropsch synthesis device top and produces the C that reclaims the tail gas except that comprising primary product Fischer-Tropsch wax from Fischer-Tropsch synthesis device output, high temperature condensation product (also claiming hot trap material), cryogenic condensation thing (also claiming the cold-trap material)
5 +Liquid product.
Described Fischer-Tropsch synthetic is through synthetic hydrocarbon and the derivative thereof that is produced of Fischer-Tropsch.
Described Fischer-Tropsch synthetic mainly contains alkane, particularly normal paraffin, also contains alkene and hydrocarbon oxide.
Contain a kind of heavier cut in the described Fischer-Tropsch synthetic, its boiling range is: 80～720 ℃.
Also contain a kind of heavier cut in the described Fischer-Tropsch synthetic, its boiling range is: 80～520 ℃.
Contain a kind of lighter cut in the described Fischer-Tropsch synthetic, its boiling range is: 42～400 ℃.
Also contain a kind of lighter cut in the described Fischer-Tropsch synthetic, its boiling range is: 42～350 ℃.
By the petroleum naphtha that Fischer-Tropsch synthetic is produced, because alkane, particularly normal paraffin content height, hydrogen-carbon ratio is the petroleum naphtha height relatively generally, and seldom contains impurity such as sulphur, nitrogen, aromatic hydrocarbons, is the raw material of fine steam pyrolysis system ethene.Therefore, exploitation synthesizes the gelatin liquefaction technology of core with Fischer-Tropsch, when producing oil fuel with Fischer-Tropsch synthetic, produces steam pyrolysis system ethylene unit naphtha materials special, not only can alleviate China's oil fuel situation in short supply, can also remedy the deficiency of ethylene raw.
Description of drawings
Fig. 1 is technological process of production figure of the present invention, and a kind of method with Fischer-Tropsch synthetic production ethylene unit naphtha materials special of the present invention can be passed through this flow implementation, but is not limited only to this flow process.Wherein equipment and pipeline are described as follows:
A: the Fischer-Tropsch synthesis device,
B: the Fischer-Tropsch synthetic hydrotreating reactor,
C: the Fischer-Tropsch synthetic hydrocracking reactor,
D: through the Fischer-Tropsch synthetic fractionator of hydrotreatment,
E: through the Fischer-Tropsch synthetic fractionator (also can contain Fischer-Tropsch synthetic) of hydrocracking through hydrotreatment;
1, the synthetic light ends dereaction device B pipeline of Fischer-Tropsch,
2, Fischer-Tropsch synthetic heavy cut dereaction device C pipeline,
3, Fischer-Tropsch synthetic heavy cut dereaction device B pipeline,
4, the Fischer-Tropsch synthetic after the hydrotreatment removes fractionator D pipeline,
5, the Fischer-Tropsch synthetic dereaction device C pipeline after the hydrotreatment,
6, Fischer-Tropsch synthetic removes fractionator E pipeline after the hydrotreatment,
7, fractionator D gained gas products goes out the device line of pipes,
8, fractionator D gained petroleum naphtha goes out the device line of pipes,
9, fractionator D gained intermediate oil device line of pipes,
10, fractionator D gained heavy ends dereaction device C pipeline,
11, the Fischer-Tropsch synthetic through hydrocracking removes fractionator E pipeline,
12, fractionator E gained gas products goes out the device line of pipes,
13, fractionator E gained petroleum naphtha goes out the device line of pipes,
14, fractionator E gained intermediate oil goes out the device line of pipes,
15, fractionator E gained heavy ends dereaction device C pipeline.
Embodiment
Below in conjunction with Fig. 1 specific implementation method of the present invention is described further.
Usually there are three kinds from the primary product of Fischer-Tropsch synthesis device output: 1) a kind of heavier cut, its boiling range is: 80～720 ℃, be called Fischer-Tropsch wax; 2) another kind of heavier cut, its boiling range is: 80～520 ℃, be called the high temperature condensation product, also claim hot trap material; 3) a kind of lighter cut, its boiling range is: 42～400 ℃, be called the cryogenic condensation thing, also claim the cold-trap material.The present invention is a kind of, and to produce the method for ethylene unit naphtha materials special with Fischer-Tropsch synthetic raw materials used except that comprising above three kinds of Fischer-Tropsch synthetics, also comprises the C that produces from Fischer-Tropsch synthesis device top the tail gas through the cryogenic freezing recovery
5 +Liquid product, its boiling range is: 42～350 ℃.
In above-mentioned Fischer-Tropsch synthetic, be mainly C
5Above, based on the hydro carbons of normal paraffin, also contain part alkene and hydrocarbon oxide etc.
Characteristics according to Fischer-Tropsch synthetic, the product that its four kinds of different fractions can be formed mixes by a certain percentage delivers to hydrotreating reactor B by pipeline 1 and pipeline 3, also can be according to the characteristics of Fischer-Tropsch synthetic different fractions, wherein lighter cut is delivered to hydrotreating reactor B by pipeline 1, and wherein heavier cut is then directly delivered to hydrocracking reactor C by pipeline 2.
In hydrotreating reactor B, hydrogenation protecting agent and Hydrobon catalyst are housed, these catalyzer can be selected the catalyzer that is used for the petroleum fractions hydrotreatment for use, also can it be improved according to the characteristics of Fischer-Tropsch synthetic and the requirement of purpose product.
Under the effect of hydrogenation protecting agent and Hydrobon catalyst, Fischer-Tropsch synthetic can be in hydrotreating reactor, under the condition that has hydrogen to exist, removes impurity such as the oxygen that wherein contains, sulphur, and is simultaneously that alkene is saturated.
Fischer-Tropsch synthetic through hydrotreatment can be delivered to hydrocracking reactor C by pipeline 5, with macromolecular hydrocarbon cracking, improves lighting end and middle runnings product yield with further.Also can deliver to Fischer-Tropsch synthetic fractionator D by pipeline 4 through hydrotreatment, what obtain after fractionation delivers to hydrocracking reactor C than last running by pipeline 10 and carries out further cracking, lighter fraction can be divided into gas, petroleum naphtha and middle runnings oil production, respectively by pipeline 7,8,9 carrying devices.Also can not establish independent fractionator D from the Fischer-Tropsch synthetic that hydrotreating reactor B comes out through hydrotreatment, and be transported to hydrocracking reaction product fractionator E by pipeline 6, mix with the Fischer-Tropsch synthetic hydrocracking product that pipeline 11 transports, be separated into enabled production gas, petroleum naphtha and middle runnings oil production in fractionator E, the heavy ends at the bottom of the tower loops back hydrocracking reactor C by pipeline 15.
According to the path combination of Fig. 1, the charging of Fischer-Tropsch synthetic hydrocracking reactor C can have following several form:
(1) heavy recycle stock of the fractionator F that transports of heavy ends+pipeline 15 of transporting of pipeline 2 from the fractionator D that transports than last running+pipeline 10 in the Fischer-Tropsch synthetic of reactor A.
(2) heavy recycle stock of the fractionator F that transports of product+pipeline 15 of transporting of pipeline 2 from the reactor B that transports than last running+pipeline 5 in the Fischer-Tropsch synthetic of reactor A.
(3) the heavy recycle stock that transports of pipeline 2 from the fractionator F that transports than last running+pipeline 15 in the Fischer-Tropsch synthetic of reactor A.
(4) heavy recycle stock of the fractionator F that transports of fractionator heavy ends+pipeline that D produces 15 of transporting of pipeline 10.
(5) product+pipeline 15 of the reactor B that transports of pipeline 5 transports the heavy recycle stock of fractionator F.
(6) pipeline 15 transports the heavy recycle stock of fractionator F.
In hydrocracking reactor, hydrocracking catalyst is housed, these catalyzer can be selected the catalyzer that is used for the petroleum fractions hydrocracking for use, also can it be improved according to the characteristics of Fischer-Tropsch synthetic and the requirement of purpose product.
Used hydrocracking catalyst is the dual-function catalyst with hydrogenation activity and lytic activity, and its hydrogenation activity is from metal component, and they can be the precious metals of VIII family in the periodic table of elements, as platinum, palladium etc.Also can be base metal, as metal M o, the W of group vib in the periodic table of elements, the Co of VIII family, Ni etc.; Lytic activity derives from the acidic components of carrier, mainly is amorphous silicon aluminium and molecular sieve.By the hydrogenation active metals components selection, support acidity components selection, modification processing and surface properties modulation can be designed the different hydrocracking catalyst of performance, satisfy the demand of different material, products scheme and technological process.Be mainly amorphous silicon aluminium for support acidity component of the present invention, also necessarily the addition portion fractionated molecule sieves.
According to producing purpose product is the requirement of petroleum naphtha, but the reactive metal of modulation hydrocracking catalyst and acid carrier, and reasonable red-tape operati condition, make it to be fit to mass production fine petroleum naphtha.
As mentioned above, Fischer-Tropsch synthetic through hydrotreatment and hydrocracking, can deliver to fractionator D, E by pipeline 4 and 11 respectively, also can deliver to fractionator E together mixing with Fischer-Tropsch synthetic in the pipeline 11 by pipeline 6 through hydrocracking through the Fischer-Tropsch synthetic of hydrotreatment.Can obtain full boiling point (FBP) at the light weight fluid product below 200 at fractionator, be fine ethylene unit naphtha materials special, can by pipeline 8 and (or) 13 outputs.Portion gas (pipeline 7 and (or) 12 is arranged simultaneously), middle runnings oil ingredient (pipeline 9 and (or) 14).The mink cell focus that fractionation obtains then by pipeline 15 and (or) 10, loop back hydrocracking reactor C, further cracking.
In the naphtha fraction of the present invention according to Fischer-Tropsch synthetic production, alkane and normal paraffin content height, the general relatively petroleum naphtha height of hydrogen-carbon ratio, and the characteristics that seldom contain impurity such as sulphur, nitrogen, aromatic hydrocarbons, by preferred hydrotreatment and hydrocracking catalyst and operational condition thereof, produce the naphtha materials special of steam pyrolysis system ethene.When producing oil fuel, for the naphtha fraction that is produced finds best application approach with Fischer-Tropsch synthetic.Can alleviate China's oil fuel situation in short supply, the deficiency of Mi moisturizing preparing ethylene by steam cracking raw material makes the Fischer-Tropsch synthetic technology that synthesizes core with Fischer-Tropsch of exploitation possess higher economic results in society.
The synthetic wax that is produced of Fischer-Tropsch, high temperature condensation product, cryogenic condensation thing are reached the C that reclaims from tail gas
5 +Liquid product is 10: 6: 2 by weight: 1 mixed, it mixes oil properties and sees Table 1.Mixing raw material is fed hydrotreating reactor, volume space velocity 4.0h when 380 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0MPa, hydrogen to oil volume ratio 1200, liquid
-1Condition under carry out hydrotreatment, hydrotreatment reaction product and hydrocracking reaction product are mixed into fractionator.4 strands of cuts of output from fractionator: 1, gas 2, C
5～200 ℃ of liquid distillates, 200～370 ℃ of liquid distillates,＞370 ℃ of tail oils.Wherein,＞370 ℃ of tail oils loop back hydrocracking reactor, C
5～200 ℃ of liquid distillates are purpose product petroleum naphtha.
The reaction conditions of hydrocracking is: volume space velocity 2.0h when 430 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0MPa, hydrogen to oil volume ratio 1600, liquid
-1Install total product distributed data and see 2, the naphtha fraction character of producing sees Table 3.
With naphtha fraction that above-mentioned experiment is produced is raw material, does the experiment of steam pyrolysis system ethene, the results are shown in table 4.
Table 1, embodiment 1 mixing raw material character
| Project | Index |
| Density (20 ℃), g/cm
3Oxygen level, the wt% sulphur content, the PPm nitrogen content, the PPm boiling range, | 0.8022 0.86 5.0 4.3 58 202 300 367 455 553 596 669 |
The product of table 2, embodiment 1 device distributes
| Cut | Content, wt% |
| Gas C 5200～370 ℃ of liquid distillates of～200 ℃ of liquid distillates | 2.1 27.8 70.1 |
Table 3, the embodiment 1 petroleum naphtha character of producing
| Project | Index |
| Density (20 ℃), g/cm 3Group composition (PONA value), wt% alkane normal paraffin alkene aromatic hydrocarbon ring alkane sulphur content, the PPm boiling range, ℃ IBP FBP | 0.7125 96.5 72.5 ＜1.0 ＜1.0 2.27 ＜0.05 62 200 |
Table 4, the embodiment 1 petroleum naphtha steam pyrolysis test-results of producing
| The steam pyrolysis productive rate, wt% | |
| The total triolefin of ethylene, propylene divinyl | 35.54 21.17 4.4 61.11 |
Adopt the mixing raw material identical, mixing raw material is fed hydrotreating reactor, volume space velocity 3.0h when 320 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 9.0MPa, hydrogen to oil volume ratio 1000, liquid with embodiment 1
-1Condition under carry out hydrotreatment, the hydrotreatment reaction product enters the Fischer-Tropsch synthetic fractionator through hydrotreatment, fractionation is 4 strands of cuts: 1, gas 2, C
5～200 ℃ of liquid distillates, 200～320 ℃ of liquid distillates,＞320 ℃ of tail oils.Wherein,＞320 ℃ of tail oils enter hydrocracking reactor, contact with hydrocracking catalyst therein, under the condition that hydrogen exists, carry out hydrocracking reaction, reaction conditions is: volume space velocity 2.0h when 400 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 9.0MPa, hydrogen to oil volume ratio 1200, liquid
-1Isocrackate advances the Fischer-Tropsch synthetic fractionator through hydrotreatment, and fractionation is 4 strands of cuts: 1, gas 2, C
5～200 ℃ of liquid distillates, 200～370 ℃ of liquid distillates,＞370 ℃ of tail oils.C
5～200 ℃ of liquid distillates are purpose product petroleum naphtha, and＞370 ℃ of tail oils turn back to hydrocracking reactor as turning oil.
Will be through the Fischer-Tropsch synthetic C that fractionator produces of hydrotreatment
5～200 ℃ of liquid distillate naphtha fractions and Fischer-Tropsch synthetic C that fractionator produces through hydrocracking
5～200 ℃ of liquid distillate naphtha fractions mix, and must mix petroleum naphtha.
Install total product distributed data and see 5, the mixing petroleum naphtha character of producing sees Table 6.
Being produced the mixing petroleum naphtha with above-mentioned experiment is raw material, does the experiment of steam pyrolysis system ethene, the results are shown in table 7.
The product of table 5, experimental example 2 devices distributes
| Cut | Content, wt% |
| Gas C 5200～370 ℃ of liquid distillates of～200 ℃ of liquid distillates | 1.8 25.9 72.3 |
Table 6, embodiment 2 produce and mix petroleum naphtha character
| Project | Index |
| Density (20 ℃), g/cm 3Group composition (PONA value), wt% alkane normal paraffin alkene aromatic hydrocarbons | 7.312 98.5 80.5 ＜1 ＜1 |
| The naphthenic hydrocarbon sulphur content, the PPm boiling range, ℃ IBP FBP | ＜1 ＜0.05 56 200 |
Table 7, embodiment 2 produce and mix petroleum naphtha steam pyrolysis test-results
| The steam pyrolysis productive rate, wt% | |
| The total triolefin of ethylene, propylene divinyl | 40.65 19.30 5.00 64.3 |
The synthetic high temperature condensation product that is produced of Fischer-Tropsch, cryogenic condensation thing are reached the C that reclaims from tail gas
5 +Liquid product is 5: 2: 1 mixed by weight, and it mixes oil properties and sees Table 8.Mixing raw material is fed hydrotreating reactor, volume space velocity 5.0h when 260 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 7.0MPa, hydrogen to oil volume ratio 800, liquid
-1Condition under carry out hydrotreatment, the hydrotreatment reaction product enters the Fischer-Tropsch synthetic fractionator through hydrotreatment, fractionation is 4 strands of cuts: 1, gas 2, C
5～200 ℃ of liquid distillates, 200～320 ℃ of liquid distillates,＞320 ℃ of tail oils.Wherein,＞320 a ℃ tail oil enters hydrocracking reactor.
With Fischer-Tropsch synthetic wax (character sees Table 8) with produce through the Fischer-Tropsch synthetic fractionator of hydrotreatment＞320 ℃ of tail oils are mixed into hydrocracking reactor, contact with hydrocracking catalyst therein, under the condition that hydrogen exists, carry out hydrocracking reaction, reaction conditions is: volume space velocity 0.5h when 370 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 7.0MPa, hydrogen to oil volume ratio 1200, liquid
-1Isocrackate advances the Fischer-Tropsch synthetic fractionator through hydrotreatment, and fractionation is 4 strands of cuts: 1, gas 2, C
5～200 ℃ of liquid distillates, 200～370 ℃ of liquid distillates,＞370 ℃ of tail oils.C
5～200 ℃ of liquid distillates are purpose product petroleum naphtha, and＞370 ℃ of tail oils turn back to hydrocracking reactor as turning oil.
Will be through the Fischer-Tropsch synthetic C that fractionator produces of hydrotreatment
5～200 ℃ of liquid distillate naphtha fractions and Fischer-Tropsch synthetic C that fractionator produces through hydrocracking
5～200 ℃ of liquid distillate naphtha fractions mix, and must mix petroleum naphtha.
Install total product distributed data and see 9, the mixing petroleum naphtha character of producing sees Table 10.
Being produced the mixing petroleum naphtha with above-mentioned experiment is raw material, does the experiment of steam pyrolysis system ethene, the results are shown in table 11.
Table 8, embodiment 3 feedstock properties
| Project | Mixing oil | Fischer-Tropsch wax |
| Density (20 ℃), g/cm
3Oxygen level, the wt% sulphur content, the PPm nitrogen content, the PPm boiling range, | 0.7701 0.98 2.0 1.8 53 183 210 287 318 380 445 506 | 0.8291 ＜0.5 8.0 6.5 85 360 429 473 509 583 625 677 |
The product of table 9, embodiment 3 devices distributes
| Cut | Content, wt% |
| Gas C 5200～370 ℃ of liquid distillates of～200 ℃ of liquid distillates | 2.0 24.5 73.5 |
Table 10, embodiment 3 produce and mix petroleum naphtha character
| Project | Index |
| Density (20 ℃), g/cm 3Group composition (PONA value), wt% alkane normal paraffin alkene aromatic hydrocarbon ring alkane sulphur content, the PPm boiling range, ℃ IBP FBP | 0.7304 97.5 69.5 ＜1 ＜1 ＜1 ＜0.05 55 200 |
Table 11, embodiment 3 produce and mix petroleum naphtha steam pyrolysis test-results
| The steam pyrolysis productive rate, wt% | |
| The total triolefin of ethylene, propylene divinyl | 38.21 23.0 4.6 65.81 |
Claims (9)
1. method of producing the ethylene unit naphtha materials special with Fischer-Tropsch synthetic is characterized in that this method may further comprise the steps:
(1) Fischer-Tropsch synthetic is whole or lighter part cut carries out hydrotreatment, and the condition of hydrotreatment is: 260～400 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0～18MPa, volume space velocity 0.1～15h during liquid
-1, hydrogen to oil volume ratio 200～1600;
(2) will partly or entirely and/or without the heavier part cut of the Fischer-Tropsch synthetic of hydrotreatment carry out hydrocracking through the Fischer-Tropsch synthetic of hydrotreatment, the condition of hydrocracking is: 300～460 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0～18MPa, volume space velocity 0.1～10h during liquid
-1, hydrogen to oil volume ratio 500～2400;
(3) product of fractionation hydrotreatment and hydrocracking gained or both mixtures, can obtain gas, light ends, middle runnings and heavy ends, wherein heavy ends turns back to hydrocracking reactor as turning oil, and light ends is the ethylene unit naphtha materials special.
2. method of producing the ethylene unit naphtha materials special with Fischer-Tropsch synthetic according to claim 1, it is characterized in that, the index of described ethylene unit naphtha materials special is: alkane content is greater than 70wt%, normal paraffin is greater than 40wt%, sulphur content is less than 0.05wt%, and full boiling point is below 200 ℃.
3. method of producing the ethylene unit naphtha materials special with Fischer-Tropsch synthetic according to claim 1, it is characterized in that, described Fischer-Tropsch synthetic also claims hot trap material, cryogenic condensation thing also to claim the cold-trap material except that comprising from primary product Fischer-Tropsch wax, the high temperature condensation product of Fischer-Tropsch synthesis device output, also comprises from Fischer-Tropsch synthesis device top and produces the C that reclaims the tail gas
5 +Liquid product.
4. according to claim 1 or 3 described methods of producing the ethylene unit naphtha materials special, it is characterized in that described Fischer-Tropsch synthetic is through synthetic hydrocarbon and the derivative thereof that is produced of Fischer-Tropsch with Fischer-Tropsch synthetic.
5. according to claim 1 or 3 described methods of producing the ethylene unit naphtha materials special, it is characterized in that described Fischer-Tropsch synthetic mainly contains alkane, comprises normal paraffin, also contain alkene and hydrocarbon oxide with Fischer-Tropsch synthetic.
6. according to claim 1 or 3 described methods of producing the ethylene unit naphtha materials special, it is characterized in that contain a kind of cut of Fischer-Tropsch wax in the described Fischer-Tropsch synthetic, its boiling range is: 80～720 ℃ with Fischer-Tropsch synthetic.
7. according to claim 1 or 3 described methods of producing the ethylene unit naphtha materials special, it is characterized in that also contain a kind of cut of hot trap material in the described Fischer-Tropsch synthetic, its boiling range is: 80～520 ℃ with Fischer-Tropsch synthetic.
8. according to claim 1 or 3 described methods of producing the ethylene unit naphtha materials special, it is characterized in that contain a kind of cut of cold-trap material in the described Fischer-Tropsch synthetic, its boiling range is: 42～400 ℃ with Fischer-Tropsch synthetic.
9. according to claim 1 or 3 described methods of producing the ethylene unit naphtha materials special, it is characterized in that, also contain a kind of C that reclaims through cryogenic freezing the tail gas that produces from Fischer-Tropsch synthesis device top in the described Fischer-Tropsch synthetic with Fischer-Tropsch synthetic
5 +The cut of liquid product, its boiling range is: 42～350 ℃.
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| CN101230291B (en) * | 2007-01-23 | 2012-02-29 | 中国石油化工股份有限公司 | Low consumption energy method for processing fischer-tropsch synthesis |
| JP5367412B2 (en) | 2009-02-27 | 2013-12-11 | 独立行政法人石油天然ガス・金属鉱物資源機構 | FT synthetic hydrocarbon purification method and FT synthetic hydrocarbon distillation separation apparatus |
| CN101812321A (en) * | 2010-03-03 | 2010-08-25 | 北京国力源高分子科技研发中心 | Fischer-Tropsch synthesis liquid fuel quality-improving processing method |
| WO2012087687A1 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Three step syngas to propylene including an intermediate conversion of byproduct ethane to propanol followed by propanol dehydration process |
| KR20170010770A (en) * | 2014-05-28 | 2017-02-01 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Fischer-tropsch gasoil fraction |
| CN105983407B (en) * | 2015-01-29 | 2018-07-13 | 中国石油天然气股份有限公司 | Cobalt-based Fischer-Tropsch synthesis catalyst for producing naphtha and drilling fluid and preparation method thereof |
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| US5885438A (en) * | 1993-02-12 | 1999-03-23 | Mobil Oil Corporation | Wax hydroisomerization process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1030251A (en) * | 1987-02-26 | 1989-01-11 | 无比石油公司 | Produce the joint hydrotreating program of high quality distilled oil or lubricating oil |
| US5885438A (en) * | 1993-02-12 | 1999-03-23 | Mobil Oil Corporation | Wax hydroisomerization process |
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Assignee: Shaanxi Weilai Energy Chemical Co., Ltd. Assignor: Shanghai Yankuang Energy Source Science and Technology Research Development Co. Contract record no.: 2012310000007 Denomination of invention: Process for preparing naphtha materials special for ethylene production device by using Fisher-Tropsch synthetic products Granted publication date: 20070131 License type: Common License Open date: 20051123 Record date: 20120111 |