CN100408655C - Preparation method of initiating solvent for direct liquefy of coal - Google Patents
Preparation method of initiating solvent for direct liquefy of coal Download PDFInfo
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- CN100408655C CN100408655C CNB200610083582XA CN200610083582A CN100408655C CN 100408655 C CN100408655 C CN 100408655C CN B200610083582X A CNB200610083582X A CN B200610083582XA CN 200610083582 A CN200610083582 A CN 200610083582A CN 100408655 C CN100408655 C CN 100408655C
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Abstract
The present invention relates to a preparation method of coal direct liquefied initial solvent, which comprises the following steps: petroleum fractions are used as raw materials, coal direct liquefied initial solvent is prepared by a catalytic hydrogenation process, wherein the distillation range of the petroleum fractions is from 220 to 538 DEG C, the specific gravity is 1.01 to 1.10 g/cm<3>, and the condensed nucleus aromatic content is larger than 70 wt%; the specific gravity of the coal direct liquefied initial solvent is from 0.95 to 0.99 g/cm<3>, the distillation range is from 220 to 480 DEG C, and the condensed nucleus aromatic content is larger than 80 wt%. The method can provide an important guarantee for successful operation of large scale coal direct liquefaction industrial devices, prepared initial solvent has good hydrogen supply performance and proper viscidity, and slurry-forming performance and conveying performance of prepared coal slurry can meet requirements of coal direct liquefaction.
Description
Technical field
The present invention relates to the DCL/Direct coal liquefaction technological process, more particularly, is a kind of preparation method who is used for the initial solvent of DCL/Direct coal liquefaction technological process.
Background technology
In the DCL/Direct coal liquefaction technological process, the effect of solvent is very important, and it reduces polyreaction by two kinds of approach.At first be physically, the free radical fragment that reaction is produced is dissolved in the solvent.Therefore, solvent need have good solubility to the heavy fragrant substance; Secondly, solvent stops second approach of polyreaction to provide hydrogen to free radical, makes it become stable molecule.In DCL/Direct coal liquefaction technology normal operation process, solvent recycles it from certain section cut of technology itself in the DCL/Direct coal liquefaction process, so also claim circulating solvent.
When the DCL/Direct coal liquefaction device brought into operation, certain solvent that use character to approach circulating solvent carried out the startup of device, and the solvent that starts usefulness is called initial solvent.In the coal tar fraction take off brilliant carbolineum or creosote is outstanding initial solvent raw material, but because their output is lower, in the startup procedure of DCL/Direct coal liquefaction scale operation device, need a large amount of initial solvents (about 30,000 tons), quantitatively be difficult to meet the demands with the brilliant carbolineum of taking off of coal tar or creosote initial solvent as bigger device.Therefore, be starved of the method for exploitation a kind of practicable preparation initial solvent, thus the needs when satisfying extensive gelatin liquefaction full scale plant and driving.
Summary of the invention
The objective of the invention is to: the preparation method of the initial solvent of a kind of DCL/Direct coal liquefaction technology is provided, when driving to satisfy extensive DCL/Direct coal liquefaction full scale plant for the needs of initial solvent.
The preparation method of initiating solvent for direct liquefy of coal provided by the present invention may further comprise the steps: be that 220-538 ℃, proportion are 1.01-1.10g/cm3 and condensed-nuclei aromatics content greater than the petroleum fractions of 70 heavy % as raw material with the boiling range, prepare initiating solvent for direct liquefy of coal by the shortening process, the proportion of described initiating solvent for direct liquefy of coal is that 0.95-0.99g/cm3, boiling range are 220-480 ℃ and the heavy % in condensed-nuclei aromatics content＞80, and the reactor that described shortening process is adopted is fixed-bed reactor or suspended-bed reactor; The hydrogenation catalyst that is adopted is the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system; The hydrogenation conditions that is adopted is as follows: temperature of reaction 330-390 ℃, reaction pressure 10-15Mpa, vapour-liquid ratio 600-1000NL/kg, air speed: 0.8-2.5h
-1
In preparation method provided by the present invention, the preferred boiling range of described raw material is that 250-480 ℃, proportion are 1.01-1.08g/cm3 and the condensed-nuclei aromatics content petroleum fractions greater than 75 heavy %, and further preferred boiling range is that 260-460 ℃, proportion are 1.01-1.06g/cm3 and the condensed-nuclei aromatics content petroleum fractions greater than 78 heavy %.
In preparation method provided by the present invention, the petroleum fractions that satisfies above-mentioned rerum natura requirement can be to be selected from one or more petroleum fractionss, for example, can be selected from: catalytic cracking recycle oil, catalytically cracked oil, aromatic hydrocarbons extract oil, long residuum, vacuum residuum, lubricating oil are extracted aromatic hydrocarbons, visbreaker tar, coking heavy oil etc. out.
The character preferred specific gravity of the described initiating solvent for direct liquefy of coal by the method for the invention preparation is that 0.96-0.98g/cm3, boiling range are 220-450 ℃ and the heavy % in condensed-nuclei aromatics content＞80.
In preparation method provided by the present invention, the condensed-nuclei aromatics content of described initiating solvent for direct liquefy of coal is satisfying under the prerequisite of above-mentioned condition, the content sum of preferred mononuclear aromatics and double ring arene is greater than 50 heavy %, and the content sum of Fourth Ring and five rings aromatic hydrocarbons is less than 3 heavy %.
In preparation method provided by the present invention, the character of the initiating solvent for direct liquefy of coal that obtains according to raw material properties and expectation can repeat shortening for same raw material, for example, repeat shortening operation 1-5 time, preferred 1-4 time, most preferably 2-3 time.
The beneficial effect of the method for the invention is mainly reflected in following aspect:
(1) raw material sources of the initial solvent of preparation gelatin liquefaction are extensive and cheap, and the petroleum fractions that possesses feedstock property of the present invention all can be used as raw material of the present invention.
(2) the method for the invention can adopt reactor pattern, operational condition and the catalyzer of unifining process, thereby relies on sophisticated oil hydrogenation treating processes.
(3) the method for the invention has certain flexibility of operation, can determine corresponding hydrogenation conditions and circulation hydrogenation number of times according to selected feedstock property.
(4) the method for the invention provides important leverage for the operation of extensive DCL/Direct coal liquefaction full scale plant from now on, prepared initial solvent has good hydrogenation performance and suitable viscosity, and the sludge forming performance of the coal slurry of being prepared and transportation performance all can satisfy the requirement of gelatin liquefaction.
Description of drawings
Fig. 1 is the schematic flow sheet of method provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction, but therefore the present invention is not subjected to any restriction.
As shown in Figure 1, petroleum fractions as raw material is at first allocated vulcanizing agent dimethyl disulfide (DMDS) in raw material batch tank 1, its ratio of allocating into is the 1.5wt% of raw material, be delivered in the test tank 3 by low pressure recycle pump 2 then, and deliver to through low pressure recycle pump 4 and high-pressure circulation pump 5 and to carry out preheating in the feed preheater 6; Hydrogen through hydrogen gas compressor 8 and hydrogen preheater 7 boosts and preheating after, with the together incoming stock preheater 6 of raw material; The temperature of charge in preheater exit is generally about 200 ℃; Raw material enters with the top of hydrogen from fixed bed hydrogenation reactor 9, carries out hydrogenation reaction; After reaction finishes, draw reaction product and make it enter high-temperature separator 10 (abbreviation high score) from reactor bottom, the temperature of high score is about 150 ℃, solvent behind the overwhelming majority hydrogenation separates at high score with gas, gas is through low-temperature separator 13 (being called for short low the branch) back part metering emptying, and is most of through recycling after circulating hydrogen compressor 17 compressions; Solvent behind the hydrogenation reclaims through high-temperature separator reducing valve 11 and product receiving tank 12; In low-temperature separator 13, the water that is generated enters through low-temperature separator reducing valve 14 and generates water receiving tank 15; For the salt that prevents to produce at gas piping crystallization blocking pipe, inject small quantity of deionized water from low subentry and wash the salt crystallization off, described deionized water injects through high pressure water-injection pump 16.Got the solvent samples of hydrogenation front and back in per 12 hours, measure their density, ultimate analysis, nmr analysis and carry out the calculating of aromaticity.
In order further to verify initial solvent preparation provided by the present invention, adopt the raw material of Anqing catalytic cracking recycle oil through aromatic hydrocarbons extraction oil (hereinafter to be referred as " Anqing aromatic hydrocarbons extraction oil ") the conduct preparation initiating solvent for direct liquefy of coal of aromatic extraction unit production.
Table 1 is the analytical data that boiling range, density, viscosity and the hydrocarbon system of above-mentioned Anqing aromatic hydrocarbons extraction oil forms.From this table as can be seen, Anqing aromatic hydrocarbons extraction oil has that density is big, boiling point is high and distributes relatively concentrates viscosity height under (300-450 ℃), the low temperature (30 ℃ time up to 745 centipoises), aromaticity content up to about 85% characteristics, thereby is a kind of raw material for preparing initiating solvent for direct liquefy of coal.
Table 1
| Anqing aromatic hydrocarbons extraction oil | |
| Boiling range: ℃ HK/10% 30% 50% 70% 90% 95%/KK | 289/365 380 388 395 414 -/454 |
| Density, g/cm 3 | 1.0758 |
| Form heavy % stable hydrocarbon aromatic hydrocarbons colloid, bituminous matter | 10.4 86.3 3.3 |
| Viscosity, centipoise, 100 ℃ | 6-9 |
| Viscosity, centipoise, 80 ℃ | 23 |
| Viscosity, centipoise, 60 ℃ | 60 |
| Viscosity, centipoise, 50 ℃ | 114 |
| Viscosity, centipoise, 40 ℃ | 274 |
| Viscosity, centipoise, 30 ℃ | 745 |
Table 2
| Anqing extraction oil | Circulating solvent before the hydrogenation | Circulating solvent behind the hydrogenation | |
| Density (20 ℃), g/cm 3 | 1.057 | 1.008 | 0.9685 |
| Hydrocarbon composition, heavy % | |||
| Paraffinic hydrocarbons | 2.0 | 8.5 | 10.7 |
| Total naphthenic hydrocarbon | 4.5 | 11.5 | 13.4 |
| Total mononuclear aromatics | 6.1 | 26.0 | 36.2 |
| Total double ring arene | 13.2 | 21.3 | 20.7 |
| Total thrcylic aromatic hydrocarbon | 22.5 | 7.1 | 9.5 |
| Total Fourth Ring aromatic hydrocarbons | 29.2 | 5.0 | 3.9 |
| Total five rings aromatic hydrocarbons | 2.4 | 0.9 | 0.7 |
| Total thiophene | 7.0 | 2.3 | 3.2 |
| Do not identify aromatic hydrocarbons | 5.7 | 1.9 | 1.7 |
| Colloid | 7.4 | 15.5 | 0.0 |
| Gross weight (containing colloid) | 100.0 | 100.0 | 100.0 |
| Total aromatic hydrocarbons | 86.1 | 64.5 | 75.9 |
| Ultimate analysis: C, wt% H, wt% N, wt% H/C atomic ratio | 89.62 7.58 1.21 1.015 | 87.83 10.14 0.50 1.385 | 88.36 11.04 0.17 1.499 |
Table 2 is contrast tables of the analytical data of mass spectrum of Anqing aromatic hydrocarbons extraction oil and a kind of DCL/Direct coal liquefaction circulating solvent.As can be seen from Table 2, compare with the DCL/Direct coal liquefaction circulating solvent, Anqing aromatic hydrocarbons extraction oil has the high characteristics of polycyclic aromatic hydrocarbon content.The content of the polycyclic aromatic hydrocarbons in the extraction oil of Anqing more than three rings accounts for 66.8%, and the above polycyclic aromatic hydrocarbon content of three rings only accounts for 19.0% in the circulating solvent.And the content of the content of the total mononuclear aromatics of Anqing extraction oil and double ring arene is more much lower than circulating solvent, the former only be 19.3% and the latter up to 56.9%.The component that the hydrogen supply performance is stronger in the DCL/Direct coal liquefaction solvent mostly is with the mononuclear aromatics of naphthane similar with the double ring arene of the luxuriant and rich with fragrance similar of dihydro.So have the hydrogenation of aromatics content of the strong hydrogen supply capacity circulating solvent height that is far from the extraction oil of Anqing.In addition, from the ultimate analysis of solvent, the H/C atomic ratio of circulating solvent is 1.499, and the H/C atomic ratio of Anqing extraction oil is 1.015.In order to make Anqing extraction oil have comparatively ideal hydrogen supply capacity when the initiating solvent for direct liquefy of coal, make its performance more approach the circulating solvent of DCL/Direct coal liquefaction process, need to adopt method provided by the present invention that Anqing aromatic hydrocarbons extraction oil is carried out appropriate hydrogenation fractional saturation and handle.Viscosity was very big when another characteristics of Anqing aromatic hydrocarbons extraction oil were low temperature, directly can make the viscosity of coal slurry bigger with its preparation coal slurry, will cause normal pressure coal slurry recycle pump and the high-pressure coal slurry transferpump can't works better in the preparation of coal slurry with in carrying.So for Anqing aromatic hydrocarbons extraction oil, one of purpose of Anqing aromatic hydrocarbons extraction oil shortening is the content that increases total hydrogenation of aromatics, improves the hydrogen supply capacity of solvent; Two of purpose is to reduce the viscosity of solvent by hydrogenation, and then reduces the viscosity of coal slurry.Also listed the composition of circulating solvent before hydrogenation in the table 2, by contrast as can be seen, polycyclic aromatic hydrocarbons minimizing generally behind the circulating solvent hydrogenation, paraffinic hydrocarbons, naphthenic hydrocarbon increase, the amplification maximum of mononuclear aromatics, and two rings, thrcylic aromatic hydrocarbon change not obvious.
In experimentation, adopt medium-sized fixed bed hydrogenation device that above-mentioned Anqing extraction oil is carried out 4 circulation hydrotreatments, so that controlledly increase the content of hydrogenation of aromatics in the solvent cut, improve the hydrogen supply capacity of solvent.Concrete hydroconversion condition is referring to table 3.The modified form hydrogenation catalyst that the hydrogenation catalyst that is adopted is produced for Japan, its trade names are CH0401, its character is referring to table 4.
Table 3
| The cyclical operation number of times | For the first time | For the second time | For the third time | The 4th time |
| Hydrogenation pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Temperature of reaction, ℃ | 340 | 340 | 340 | 340 |
| Apparent air speed, h -1 | 0.7 | 0.7 | 0.7 | 0.7 |
| Solvent flux, kg/h | 6.8 | 6.8 | 6.8 | 6.8 |
| New hydrogen flow, Nm 3/h | 2.5 | 2.5 | 2.5 | 2.5 |
| The recycle hydrogen flow, Nm 3/h | 3.3 | 3.3 | 3.3 | 3.3 |
| Gas/liquid, 1/kg | 830 | 830 | 830 | 830 |
| DMDS addition *, % | 1.5 | 1.5 | 1.5 | 1.5 |
| The high score temperature, ℃ | 110 | 110 | 110 | 110 |
| Water injection rate, kg/h | 0.42 | 0.42 | 0.42 | 0.42 |
* this parameter is the weight ratio of solvent before vulcanizing agent dimethyl disulfide and the hydrogenation
Table 4
With Anqing extraction oil shown in the table 1 is raw material, the hydrotreatment that circulates according to the method described in the present invention, and operating process is summarized as follows: allocate vulcanizing agent dimethyl disulfide (DMDS) in the raw material into, the ratio of allocating into is the 1.5wt% of raw material; Raw material before the hydrogenation arrives preheater 6 through high-pressure pump 5 through preparation of raw material jar 1 again to test tank 2, and the temperature out of preheater is about 200 ℃; Raw material advances reactor with hydrogen from the top of fixed bed hydrogenation reactor 9, carries out the solvent hydrogenation reaction; After reaction finishes, the reaction product of coming out from reactor bottom enters high-temperature separator 10, the temperature of high score is 110 ℃, solvent behind the overwhelming majority hydrogenation separates at high score with gas, gas is through low-temperature separator 13 back part metering emptying, and is most of through recycling after circulating hydrogen compressor 17 compressions; For the salt that prevents to produce at gas piping crystallization blocking pipe, inject small quantity of deionized water from low subentry and wash the salt crystallization off; Got the solvent samples of hydrogenation front and back in per 12 hours, measure their density, ultimate analysis, nmr analysis and carry out the calculating of aromaticity.
Table 5 is to be the changing conditions of 45% viscosity of coal slurry through the viscosity of Anqing aromatic hydrocarbons extraction oil of different circulation hydrogenation number of times and a kind of DCL/Direct coal liquefaction circulating solvent and corresponding dry coal concentration.As can be seen from Table 5, under 40 ℃ of conditions, the aromatic hydrocarbons extraction oil viscosity is 17 times of hydrogenation circulating solvent, up to 274cp, can't measure with the viscosity of coal slurry of its preparation.Aromatic hydrocarbons extraction oil is through behind hydrogenation, and the viscosity of solvent obviously reduces, and 40 ℃ of mensuration, drops to 84cp from 274cp equally.When preparing the coal slurry of 45% concentration as solvent with a hydrogenation aromatic hydrocarbons extraction oil, the viscosity of the coal slurry that obtains in the time of 40 ℃ up to 2335cp, but, no matter be that the hydrogenation aromatic hydrocarbons extraction oil or the viscosity degradation amplitude of the coal slurry of preparing with it are very big along with the raising of temperature.Through hydrogenation repeatedly, obtain the aromatic hydrocarbons extraction oil of secondary hydrogenation and three hydrogenation, the viscosity number of the coal slurry of their viscosity and preparation 45% concentration and with more all being listed in the table 5 of hydrogenation circulating solvent.With the aromatic hydrocarbons extraction oil phase ratio of hydrogenation not, decline by a big margin through the aromatic hydrocarbons extraction oil viscosity of three hydrogenation, drop to 35cp from 274cp in the viscosity of 40 ℃ of mensuration of low temperature.Aromatic hydrocarbons extraction oil behind three hydrogenation is (four hydrogenation) behind the hydrogenation once more, and viscosity no longer includes obvious variation.Equally with the aromatic hydrocarbons extraction oil phase ratio of hydrogenation not, the viscosity of (80 ℃) under the condition of high temperature of the extraction oil viscosity behind the hydrogenation is similar substantially, and is not obvious with the hydrogenation depth relationship.The different hydrogenation degree of depth aromatic hydrocarbons extraction oil preparation coal slurry the time, low temperature (40 ℃) down viscosity of coal slurry alter a great deal, during with the aromatic hydrocarbons extraction oil coal blending slurry of hydrogenation, can not get flowable coal slurry thereby also can't measure its viscosity.With once with the viscosity of coal slurry under low temperature (40 ℃) of the aromatic hydrocarbons extraction of secondary hydrogenation oil preparation more than 2000cp, but under high temperature (80 ℃), viscosity of coal slurry is about 200cp.Although it is also have some gaps with the viscosity of coal slurry that the hydrogenation circulating solvent prepares, more approaching with the oily viscosity for preparing the coal slurry of 45% concentration of the aromatic hydrocarbons extraction of three hydrogenation.The viscosity of the coal slurry of producing with three hydrogenation aromatic hydrocarbons extraction oil when 80 ℃ and 60 ℃ is with basic identical 60 ℃ and 40 ℃ of viscosity with the coal slurry of the same concentration of hydrogenation circulating solvent preparation.When that is to say with three hydrogenation aromatic hydrocarbons extractions oil preparation coal slurries, if the preparation temperature of coal slurry can be improved 20 ℃ the time, its viscosity of coal slurry is with basic identical with the viscosity of coal slurry of hydrogenation circulating solvent preparation.Therefore,, carry pump characteristic under than higher temperature, can determine suitable hydrogenation pass, to satisfy the normal needs of carrying of coal slurry in conjunction with coal slurry recycle pump and coal slurry if the preparation of coal slurry and conveying can be carried out.
Table 6 is structural analyses of different hydrogenation passes Anqing aromatic hydrocarbons extraction oil and hydrogenation circulating solvent.As can be seen from Table 6, along with the increase of the hydrogenation degree of depth, the content of total mononuclear aromatics and total double ring arene obviously increases in the hydrogenation extraction oil, and the content of total above polycyclic aromatic hydrocarbons of thrcylic aromatic hydrocarbon reduces gradually.But during to four hydrogenation, total mononuclear aromatics content and total double ring arene content no longer increase, and the content of total naphthenic hydrocarbon obviously increases.
Table 5
Table 7 is that Anqing aromatic hydrocarbons extraction oil of different hydrogenation passes and the ultimate analysis and the aromaticity fa value of hydrogenation circulating solvent are analyzed.As can be seen from Table 7, along with the increase of aromatic hydrocarbons extraction oil hydrogenation number of times, the H/C atomic ratio of hydrogenation extraction oil continues to increase, and is increased to 1.581 from 1.015.The aromaticity of solvent also descends with the increase of hydrogenation pass.The fa value of the solvent that obtains through the secondary hydrogenation is the same substantially with the hydrogenation circulating solvent.With the character of circulating solvent with to form immediate be aromatic hydrocarbons extraction oil through three hydrogenation, their H/C atomic ratio is about 1.5.
This shortening to Anqing aromatic hydrocarbons extraction oil studies show that, the character of aromatic hydrocarbons extraction oil properties and DCL/Direct coal liquefaction hydrogenation circulating solvent is very approaching behind the hydrogenation that Anqing aromatic hydrocarbons extraction oil process shortening obtains, and Anqing aromatic hydrocarbons extraction oil behind the hydrogenation is the ideal initiating solvent for direct liquefy of coal.But the transportation performance of the coal slurry of considering the hydrogen supply performance of solvent and obtaining, at Anqing aromatic hydrocarbons extraction oil properties that is adopted in this experiment, resulting oil product is relatively more suitable to the DCL/Direct coal liquefaction starting raw material behind three circulation hydrogenation.
Table 6
| Anqing extraction oil former state | A hydrogenation extraction oil | Secondary hydrogenation extraction oil | Three hydrogenation extraction oils | Four hydrogenation extraction oils | The hydrogenation circulating solvent | |
| 20 ℃ of proportions | 1.0758 | 1.0338 | 1.016 | 0.9888 | 0.9701 | 0.9685 |
| Hydrocarbon composition, wt% | ||||||
| Paraffinic hydrocarbons | 2.0 | 1.6 | 2.4 | 3.2 | 3.0 | 10.7 |
| Total naphthenic hydrocarbon | 4.5 | 4.4 | 8.6 | 20.6 | 27.8 | 13.4 |
| Total mononuclear aromatics | 6.1 | 17.4 | 28.3 | 33.1 | 31.7 | 36.2 |
| Total double ring arene | 13.2 | 24.8 | 26.6 | 23.0 | 21.8 | 20.7 |
| Total thrcylic aromatic hydrocarbon | 22.5 | 26.9 | 18.4 | 8.4 | 5.5 | 9.5 |
| Total Fourth Ring aromatic hydrocarbons | 29.2 | 14.4 | 7.0 | 3.3 | 1.9 | 3.9 |
| Total five rings aromatic hydrocarbons | 2.4 | 1.0 | 0.5 | 0.4 | 0.5 | 0.7 |
| Total thiophene | 7.0 | 6.2 | 6.5 | 6.5 | 6.6 | 3.2 |
| Do not identify aromatic hydrocarbons | 5.7 | 3.3 | 1.7 | 1.5 | 1.2 | 1.7 |
| Colloid | 7.4 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| Gross weight (containing colloid) | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Total aromatic hydrocarbons | 86.1 | 94.0 | 89.0 | 76.2 | 69.2 | 75.9 |
Table 7
| Anqing extraction oil former state | A hydrogenation extraction oil | Secondary hydrogenation extraction oil | Three hydrogenation extraction oils | Four hydrogenation extraction oils | The hydrogenation circulating solvent | |
| C，wt％ | 89.62 | 89.33 | 10.54 | 11.05 | 11.57 | 11.04 |
| H，wt％ | 7.58 | 9.45 | 88.88 | 88.16 | 87.83 | 88.36 |
| N，wt％ | 0.87 | 0.64 | 0.26 | 0.15 | 0.01 | 0.13 |
| S，wt％ | 1.47 | 0.60 | 0.20 | 0.16 | 0.04 | 0.09 |
| The H/C atomic ratio | 1.015 | 1.269 | 1.423 | 1.504 | 1.581 | 1.499 |
| Aromaticity, fa | 0.61 | 0.52 | 0.42 | 0.36 | 0.33 | 0.43 |
Claims (9)
1. the preparation method of an initiating solvent for direct liquefy of coal, may further comprise the steps: be that 220-538 ℃, proportion are 1.01-1.10g/cm3 and condensed-nuclei aromatics content greater than the petroleum fractions of 70 heavy % as raw material with the boiling range, prepare initiating solvent for direct liquefy of coal by the shortening process, the proportion of described initiating solvent for direct liquefy of coal be 0.95-0.99g/cm3, boiling range be 220-480 ℃ and condensed-nuclei aromatics content greater than 80 heavy %, the reactor that described shortening process is adopted is fixed-bed reactor or suspended-bed reactor; The hydrogenation catalyst that is adopted is the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system; The hydrogenation conditions that is adopted is as follows: temperature of reaction 330-390 ℃, reaction pressure 10-15Mpa, vapour-liquid ratio 600-1000NL/kg, air speed: 0.8-2.5h
-1
2. according to the described preparation method of claim 1, it is characterized in that the boiling range of described raw material is that 250-480 ℃, proportion are that 1.01-1.08g/cm3 and condensed-nuclei aromatics content are greater than 75 heavy %.
3. according to the described preparation method of claim 2, it is characterized in that the boiling range of described raw material is that 260-460 ℃, proportion are that 1.01-1.06g/cm3 and condensed-nuclei aromatics content are greater than 78 heavy %.
4. according to claim 1 or 3 described preparation methods, it is characterized in that described raw material is selected from: the mixture of one or more in catalytic cracking recycle oil, catalytically cracked oil, aromatic hydrocarbons extract oil, long residuum, vacuum residuum, lubricating oil extraction aromatic hydrocarbons, visbreaker tar and the coking heavy oil.
5. according to the described preparation method of claim 4, it is characterized in that the proportion of described initial solvent is that 0.96-0.98g/cm3, boiling range are 220-450 ℃.
6. according to the described preparation method of claim 5, it is characterized in that in described initial solvent, the content sum of mononuclear aromatics and double ring arene is greater than 50 heavy %, and the content sum of Fourth Ring and five rings aromatic hydrocarbons is less than 3 heavy %.
7. according to the described preparation method of claim 1, it is characterized in that, in described shortening process, described raw material is carried out hydrofining.
8. according to the described preparation method of claim 7, it is characterized in that for same raw material, described shortening process repeats 1-4 time.
9. according to the described preparation method of claim 8, it is characterized in that described shortening process repeats 2-3 time.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068355A (en) * | 1991-07-11 | 1993-01-27 | 中国石油化工总公司石油化工科学研究院 | The manufacture method of low aromatic solvent naphtha |
| CN1769391A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Solvent oil hydrogenation and quality change method |
-
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| CN1068355A (en) * | 1991-07-11 | 1993-01-27 | 中国石油化工总公司石油化工科学研究院 | The manufacture method of low aromatic solvent naphtha |
| CN1769391A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Solvent oil hydrogenation and quality change method |
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