CN103509576A - Method for separating inorganic substances from direct coal liquefaction residues - Google Patents
Method for separating inorganic substances from direct coal liquefaction residues Download PDFInfo
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- CN103509576A CN103509576A CN201210215707.5A CN201210215707A CN103509576A CN 103509576 A CN103509576 A CN 103509576A CN 201210215707 A CN201210215707 A CN 201210215707A CN 103509576 A CN103509576 A CN 103509576A
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- liquefied residue
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- 239000003245 coal Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 title abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 73
- 239000012065 filter cake Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000605 extraction Methods 0.000 claims description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000011707 mineral Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000011302 mesophase pitch Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- -1 aromatic hydroxy compound Chemical class 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 241000772415 Neovison vison Species 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 150000007529 inorganic bases Chemical class 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000010426 asphalt Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 235000021110 pickles Nutrition 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for separating inorganic substances from direct coal liquefaction residues, which sequentially comprises the following steps of: 1) pulverizing and/or grinding the coal direct liquefaction residue to obtain fine powder with particle diameter less than 100 microns; 2) mixing the fine powder with a solvent I, and reacting for 0.5-20 hours at 20-300 ℃ under a stirring state, wherein the solvent I comprises inorganic acid with the concentration of 1-40 wt%; 3) filtering and/or centrifuging the reaction product obtained in the step (2) to obtain a filter cake I; 4) mixing the filter cake I with a solvent II, and reacting for 0.5-20 hours at 20-300 ℃ under a stirring state, wherein the solvent II comprises inorganic base with the concentration of 1-60% (by weight); 5) and (4) filtering and/or centrifuging the reaction product obtained in the step (4) to obtain a filter cake II, and then drying the filter cake II.
Description
Technical field
The present invention relates to a kind of from coal directly-liquefied residue the method for separated inanimate matter, particularly relate to and by described method, from coal directly-liquefied residue, after separated inanimate matter, obtain the method for the preparation of the mesophase pitch matter of carbon fiber.
Background technology
Direct coal liquefaction process is under high-temperature and high-pressure conditions, under catalyst action, by hydrogenation reaction, coal is converted into the coal clean technology of liquid fuel or industrial chemicals.In direct coal liquefaction process process, except obtaining liquid product, also produce the solid residue that accounts for raw coal total amount 20～30%.Effectively utilize these liquefied residues, the resource utilization of direct coal liquefaction process and economy are had to immeasurable impact.
For many years, all constantly exploring the method for utilizing coal directly-liquefied residue (DCLR) both at home and abroad, at present, utilizing the method for coal directly-liquefied residue mainly to comprise: by liquefied residue vaporizing system for synthetic gas; Liquefied residue is carried out to destructive distillation and obtain mink cell focus, retortable oil and coke; Using liquefied residue as road asphalt modifier; Liquefied residue is directly burnt as solid fuel; Preparation CNT (carbon nano-tube); With prepare mesophase pitch, carbon fibre material etc. is produced in regeneration.Particularly, in recent years, separate bitumen alkene and preasphaltene from coal directly-liquefied residue, after modification, prepare mesophase pitch, carbon fiber is produced in regeneration, the study hotspot that coal directly-liquefied residue utilizes, general method separate bitumen alkene and the preasphaltene from coal directly-liquefied residue that adopts extraction.
Yet, coal directly-liquefied residue is the material of a kind of high-carbon, high ash and high-sulfur, in coal, unconverted organic matter, inorganic mineral and additional catalyzer have thoroughly formed the main body of coal directly-liquefied residue, wherein the content of inorganic mineral and catalyzer reaches 30%, so high inanimate matter content directly affects softening temperature and the viscosity of coal directly-liquefied residue, from coal directly-liquefied residue, in the process of separate bitumen alkene and preasphaltene, improve operation easier, increased process costs.For example, CN101885976, CN101580729A, CN1948148A, CN1629257A, CN101962560A and CN101962561A disclose the technique of extracting mink cell focus and mesophase pitch or asphaltene and/or preasphaltene by the method for extraction from coal directly-liquefied residue, the extraction agent using comprises: liquefaction oil product, N, N-N,N-DIMETHYLACETAMIDE, furfural, DMF, tetrahydrofuran (THF), METHYLPYRROLIDONE, dithiocarbonic anhydride, quinoline, pyridine, toluene, tetrahydrofuran (THF) and pyridines and quinoline ionic liquid etc.Asphaltene, preasphaltene and/or the mink cell focus obtaining with described extraction agent separation can be prepared mesophase pitch through a step again by heating destructive distillation, and then produces carbon fibre material.
In using the method for extraction agent separate bitumen alkene and preasphaltene from coal directly-liquefied residue, because of the softening temperature of coal directly-liquefied residue relatively high, general employing high-temperature operation and/or high top pressure operation are melted coal directly-liquefied residue to be mixed in extraction agent, then carry out asphaltene and preasphaltene and extraction agent lock out operation, this can increase complicacy and the production cost of technique undoubtedly.
US6,717,021 disclose a kind of for dissolving the solvent composition of mesophase pitch, this composition comprises aromatic hydrocarbons mixture, its atmospheric boiling point is approximately 285-500 ℃, preferably at least 80% carbon atom is aromatize, such aromatic hydroxy compound example comprises the aromatic hydroxy compound that contains 2-5 aromatic nucleus and the replacement that contains 2-5 aromatic nucleus, hydrogenation or replaces the aromatic hydroxy compound of hydrogenation, wherein substituting group is the alkyl with 1-3 carbon atom, for example bend, dibenzphenanthrene, 5,6-dihydro bends, 1,7-dimethyl is bent, 1-methyl, 5,6-dihydro is bent etc.This solvent composition can be used for diluting the mesophase pitch of high molecular, so that its viscosity, yield temperature and melt temperature reduction, thereby when preparing carbon fiber with it, be conducive to adopt lower temperature to carry out spinning operation.
Although above-mentioned molten mixing method has saved necessary later separation step in the method for using extraction agent separate bitumen alkene, but because of the inanimate matter of high-content in coal directly-liquefied residue easily bonding with a large amount of asphaltenes, easy blocking filtering device when filter operation, need higher working pressure, and must lose a part of bituminous matter.
All disclosures of above-mentioned patent documentation are introduced with for referencial use in full at this.
For solving the problem facing in above-mentioned prior art, the inventor introduces the chemical deliming method that is mainly used in coal washing industry in this area, in coal directly-liquefied residue, inanimate matter content is higher than coal, and the content of the organic matter such as asphaltene, preasphaltene is high, and therefore the difficulty of separated inanimate matter is larger.Catalyzer in sour solvent and alkali solvent displacement and coal directly-liquefied residue and inorganic mineral qualitative response for the present invention, effectively most of inanimate matter is separated from coal directly-liquefied residue, reduced the interference of inanimate matter, thus improved coal directly-liquefied residue can utility value.Further, the inventor by adding certain density tensio-active agent and/or alcohol in sour solvent and/or alkali solvent, sour solvent or the wetting property of alkali solvent to coal directly-liquefied residue have been improved, also improved the efficiency of whole sepn process simultaneously, after pickling and/or alkali cleaning, promptly make containing organic reaction product separated with pickle solution and/or alkaline wash, obviously improve separating effect, reduced separation costs.Importantly, from coal directly-liquefied residue, removed after most of inanimate matter, during by extraction process or molten mixed method separate bitumen alkene and preasphaltene, can reduce service temperature and/or working pressure, thereby reduced running cost, and can extract more valuable carbon fiber precursor.In addition,, because containing some valuable transition metal in coal directly-liquefied residue, also can from the reaction solution that coal directly-liquefied residue and sour solvent and alkali solvent reaction obtain, reclaim transition metal if desired.
Summary of the invention
As previously mentioned, for overcoming above-mentioned prior art problem, the invention provides a kind of from coal directly-liquefied residue the method for separated inanimate matter, comprise the following steps in order:
1) pulverize and/or grind coal directly-liquefied residue, obtaining the fine powder that particle diameter is less than 100 microns;
2) above-mentioned fine powder is mixed mutually with solvent I, under whipped state, in 20～300 ℃, react 0.5～20 hour, the weight ratio of the fine powder of described solvent I and coal directly-liquefied residue is 1:1～20:1, and described solvent I comprises that concentration is 1～40(weight) mineral acid of %;
3) reaction product of step (2) is filtered and/or the centrifugal filter cake I that obtains;
4) above-mentioned filter cake I is mixed mutually with solvent II, under whipped state, in 20～300 ℃ of reactions 0.5～20 hour, the weight ratio of described solvent II and filter cake I is 1:1～20:1, described solvent II comprised that concentration is 1～60(weight) mineral alkali of %;
5) reaction product of step (4) is filtered and/or the centrifugal filter cake II that obtains, then filter cake II is dried;
6) optionally, step (2) to step (5) is repeated 1～5 time.
For improving sour solvent or alkali solvent to the wetting property of direct liquefaction residue and improving pickle solution or the separating effect of alkaline wash and reaction product, described solvent I and/or solvent II also can comprise 0.1～10(weight) tensio-active agent and/or the 0.1～10(weight of %) alcohol of %.Wherein, tensio-active agent can be selected from cats product, anion surfactant, nonionogenic tenside and their mixture; Alcohol can be selected from methyl alcohol, ethanol, propyl alcohol and their mixture.
Preferably, the operation of step (2) and/or step (4) is under the condition of pressurization, negative pressure, normal pressure or change pressure, to carry out.And the organic matter in coal directly-liquefied residue exists with liquid state or solid-state form in the reaction process of step (2) and/or step (4).
In the present invention, the mineral acid in described solvent I can be selected from hydrochloric acid, fluoric acid, silicofluoric acid, sulfuric acid, nitric acid, industrial waste acid and their mixture; And mineral alkali in described solvent II can be sodium hydroxide, ammoniacal liquor, industrial alkali waste and/or their mixture.
Preferably, the transition metal in the filtrate obtaining in step (3) and/or in the filtrate obtaining in step (5) can be reclaimed by redox reaction.
On the basis of the method in the present invention aspect first, the filter cake II obtaining in step (5) is further carried out to rectifying or extraction treatment with extraction agent, so that the asphaltene in coal directly-liquefied residue, preasphaltene and/or mink cell focus is completely separated with inanimate matter.Wherein, described extraction agent can comprise ionic liquid and/or organic solvent.
On the basis of the method in the present invention aspect first, the filter cake II obtaining in step (5) is further melted to mixed processing with the molten mixture of at least two kinds of polycomponent aromatic hydrocarbons containing the aromatic hydroxy compound of 2-5 aromatic nucleus, organic matter in filter cake II is completely separated with inanimate matter, to obtain mesophase pitch.
Direct liquefaction residue after the removal inanimate matter obtaining according to the method for separated inanimate matter of the present invention can be used for making mesophase pitch matter, through polymerization, spinning and carburising step, is used to manufacture carbon fiber.
Accompanying drawing explanation
Fig. 1 adds Sodium dodecylbenzene sulfonate (LAS) the distribution design sketch of coal directly-liquefied residue in sour solvent before in the sour solvent of the embodiment of the present invention 2.
Fig. 2 is with adding the distribution design sketch of reaction product in pickle solution after the sour solvent treatment of Sodium dodecylbenzene sulfonate (LAS) in the embodiment of the present invention 2.
Fig. 3 adds the distribution design sketch of coal directly-liquefied residue in alkali solvent before ethanol in the alkali solvent of the embodiment of the present invention 3.
Fig. 4 is with adding the distribution design sketch of reaction product in alkaline wash after the alkali solvent treatment of ethanol in the embodiment of the present invention 3.
Embodiment
By the description below with reference to accompanying drawing, be further explained in detail the present invention, but below describe only for making general technical staff of the technical field of the invention can more be expressly understood principle of the present invention and marrow, and do not mean that the present invention is carried out to any type of restriction.
Generally speaking, inanimate matter in coal directly-liquefied residue (DCLR) generally comprises salts substances and/or the oxide compound of the metals such as Al, Si, Ca, K, Fe, Mg, Ti, also may contain additional waste coal direct liquefaction catalyzer, as sulfide and/or the oxide compound of the transition metal such as molybdenum, manganese, chromium, nickel, tungsten, cobalt, iron.And organic matter in coal directly-liquefied residue mainly comprises aliphatic hydrocarbon and aromatic hydrocarbon, and aromatic hydrocarbon is the desirable feedstock of producing high-performance carbon fibre.The aromatic hydrocarbon existing in coal directly-liquefied residue is to condense aromatic hydrocarbon, it is characterized in that C/H atomic ratio is high.Such aromatic hydrocarbon or anine are limited because of weather resistance, when for the preparation of carbon fiber, estimate, before being spun into fiber, can under gentle condition, be aggregated.But be used to prepare before carbon fiber, must guaranteeing the purity of above-mentioned aromatic hydrocarbon resin.This has proposed high requirement to separation or extraction process.
In the present invention, coal directly-liquefied residue is processed successively with the solvent that contains acid or alkali, above-mentioned inanimate matter is wherein dissolved in described solvent, reach the organic matter effect effectively separated with inanimate matter in coal directly-liquefied residue.The process of separated inanimate matter from coal directly-liquefied residue, comprises following step in order:
The first step: coal directly-liquefied residue is pulverized and/or ground, obtain the fine powder that particle diameter is less than 100 microns; For improving the contact area of fine powder and solvent, preferably, particle diameter can be less than 50 microns; More preferably, particle diameter can be less than 25 microns;
Second step: above-mentioned fine powder is mixed mutually with solvent I, and described solvent I comprises that concentration is 1～40(weight) mineral acid of %; Wherein, mineral acid is selected from hydrochloric acid, fluoric acid, sulfuric acid, nitric acid, nitric acid, silicofluoric acid, industrial waste acid and their mixture; Then, its reaction product is filtered and/or the centrifugal filter cake I that obtains;
The 3rd step: above-mentioned filter cake I is mixed mutually with solvent II, and described solvent II comprises that concentration is 1～60(weight) mineral alkali of %; Wherein, mineral alkali is selected from sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, aluminium hydroxide, ammoniacal liquor, industrial alkali waste and their mixture; Then, its reaction product is filtered and/or the centrifugal filter cake II that obtains, filter cake II is dried.
In fact, can second step and the 3rd step be repeated 1～5 time according to actual requirement.Service temperature in second step and the 3rd step is 20～300 ℃, and the reaction times is 0.5～20 hour.And the pressure that working pressure in second step and the 3rd step can be selected pressurization, negative pressure, normal pressure or change in good time, pressurization and negative pressure are for normal pressure, selecting the pressure changing is to say in second step or the 3rd step to select different pressure conditions, for example normal pressure after first negative pressure, also can select the interim mode that changes the mode of pressure or progressively change pressure simultaneously.
In addition, for improving sour solvent or alkali solvent to the wetting property of coal directly-liquefied residue and improving pickle solution or the separating effect of alkaline wash and reaction product, described solvent I and/or solvent II also can comprise 0.1～10(weight) tensio-active agent and/or the 0.1～10(weight of %) alcohol of %.Wherein, tensio-active agent can be selected from cats product, anion surfactant, nonionogenic tenside and their mixture; Alcohol can be selected from methyl alcohol, ethanol, propyl alcohol and their mixture.
In the present embodiment, by above-mentioned steps separated removal after most of inanimate matter from coal directly-liquefied residue, can, by filter cake II is further carried out to rectifying or extraction treatment with extraction agent, reach asphaltene, preasphaltene and/or mink cell focus completely separated with inanimate matter; Or, by above-mentioned steps separated removal after most of inanimate matter from coal directly-liquefied residue, also can, by filter cake II is further melted to mixed processing with the molten mixture of at least two kinds of polycomponent aromatic hydrocarbons containing the aromatic hydroxy compound of 2-5 aromatic nucleus, reach organic completely separated with inanimate matter.
With the catalyzer in sour solvent and alkali solvent displacement and coal directly-liquefied residue and inorganic mineral qualitative response, effectively most of inanimate matter is separated from coal directly-liquefied residue, thereby greatly reduce inanimate matter in coal directly-liquefied residue and organic bondability, reduced the interference of inanimate matter, thereby the operational condition while making follow-up rectifying, extraction or molten mixed processing will be no longer harsh, and the operating time also will shorten greatly.Further, by add certain density tensio-active agent and/or alcohol in sour solvent and/or alkali solvent, sour solvent or the wetting property of alkali solvent to coal directly-liquefied residue have been improved, also improved the efficiency of whole sepn process simultaneously, after pickling and/or alkali cleaning, promptly make containing organic reaction product separated with pickle solution and/or alkaline wash, obviously improve separating effect, reduced separation costs.Importantly, from coal directly-liquefied residue, removed after most of inanimate matter, during by extraction process or molten mixed method separate bitumen alkene and preasphaltene, can reduce service temperature and/or working pressure, thereby reduced running cost, and can extract more valuable carbon fiber precursor.In addition,, because containing some valuable transition metal in coal directly-liquefied residue, also can from the reaction solution that coal directly-liquefied residue and sour solvent and alkali solvent reaction obtain, reclaim transition metal if desired.
Embodiment
By detailed one exemplary embodiment, further describe the present invention below, but these embodiment do not form any limitation of the invention.
Embodiment 1
Carry out according to the following steps the test of embodiment 1:
1) coal directly-liquefied residue pulverized and ground, obtaining particle diameter and be the fine powder of 1 micron;
2) the above-mentioned fine powder of 20g is added in the mineral acid solvent of 100g, wherein, described mineral acid solvent is 40% by 15 parts of HF(concentration), 45 parts of HCl(concentration are 36%) and 40 parts of deionized waters form, under normal pressure, the condition of 23 ℃, stirring reaction is 10 hours, is then washed, suction filtration obtains filter cake I;
3) the filter cake I of 1 7.1g is added in the NaOH solvent (concentration is 34%) of 100g, under normal pressure, the condition of 90 ℃, stirring reaction is 1.5 hours, is then washed, suction filtration obtains filter cake II.
4) filter cake II is dried, analyze the weight percent content of its inanimate matter and C/H ratio, result is as shown in table 1.
Table 1
| Before processing | After acid treatment | After alkaline purification | Reduction | |
| Inanimate matter, % by weight | 26.1 5 | 9.1 | 6.82 | 79.3% |
| C/H (atomic ratio) | 1.61 | 1.52 | 1.60 | 0% |
From the testing data of table 1 above, can find out: after peracid treatment and alkaline purification, the inanimate matter content in coal directly-liquefied residue reduces greatly, and C/H changes than not, and the organic matter of reaction product is still take aromatic hydrocarbon as main.
Embodiment 2
Carry out according to the following steps the test of embodiment 2:
1) coal directly-liquefied residue pulverized and ground, obtaining particle diameter and be the fine powder of 10 microns;
2) the above-mentioned fine powder of 20g is added in the hydrochloric acid soln (concentration is 36%) of 100g, the distribution effect of coal directly-liquefied residue in sour solvent is shown in Fig. 1, then add Sodium dodecylbenzene sulfonate tensio-active agent (LAS, concentration is 4%), under normal pressure, the condition of 30 ℃, stirring reaction is standing after 5 hours, now the distribution effect of coal directly-liquefied residue in pickle solution is shown in Fig. 2, and organic phase is separated with pickle solution, carries out suction filtration and obtains filter cake I;
3) the filter cake I of 15.9g is added in the NaOH solvent (concentration is 34%) of 100g, under normal pressure, the condition of 90 ℃, stirring reaction is 1.5 hours, is then washed, suction filtration obtains filter cake II.
4) filter cake II is dried, analyze the weight percent content of its inanimate matter, result is as shown in table 2.
Table 2
| Before processing | After acid treatment | After alkaline purification | Reduction | |
| Inanimate matter, % by weight | 26.1 5 | 6.62 | 5.81 | 82.6% |
From the testing data of table 2 above and Fig. 1 and Fig. 2, can find out: with adding after the sour solvent treatment of Sodium dodecylbenzene sulfonate (LAS), most of inanimate matter in coal directly-liquefied residue is removed, simultaneously, in pickle solution, organic phase and inorganic phase layering be obvious, is conducive to carry out separating treatment in step (2).
Embodiment 3
Carry out according to the following steps the test of embodiment 3:
1) coal directly-liquefied residue pulverized and ground, obtaining particle diameter and be the fine powder of 10 microns;
2) the above-mentioned fine powder of 20g is added in the mineral acid solvent of 100g, wherein, described mineral acid solvent is 40% by 15 parts of HF(concentration), 45 parts of HCl(concentration are 36%) and 40 parts of deionized waters form, under normal pressure, the condition of 23 ℃, stirring reaction is 10 hours, is then washed, suction filtration obtains filter cake I;
3) the filter cake I of 1 7.2g is added in the NaOH solvent (concentration is 34%) of 1 00g, coal directly-liquefied residue is shown in Fig. 3 in the distribution effect in alkali solvent, the ethanol (concentration is 50%) that then adds 10g, under normal pressure, the condition of 20 ℃, stirring reaction is standing after 5 hours, now the distribution effect of coal directly-liquefied residue in alkaline wash is shown in Fig. 4, and organic phase is separated with alkaline wash, suction filtration obtains filter cake II.
4) filter cake II is dried, analyze the weight percent content of its inanimate matter, result is as shown in table 3.
Table 3
| Before processing | After acid treatment | After alkaline purification | Reduction | |
| Inanimate matter, % by weight | 26.1 5 | 9.1 | 6.22 | 81.3% |
From the testing data of table 3 above and Fig. 3 and Fig. 4, can find out: in alkali solvent, add ethanol to contribute to remove inanimate matter from coal directly-liquefied residue, simultaneously, with adding after the alkali solvent treatment of ethanol, in alkaline wash, organic phase and inorganic phase layering be obvious, is conducive to carry out separating treatment in step (3).
The term that this specification sheets is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, when using these terms and form of presentation, are not intended to any equivalent exclusion of the feature that represents and describe or its integral part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary; those skilled in the art should recognize in the situation that not departing from principle of the present invention and spirit can carry out any accommodation and improvement to these embodiments, and protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (13)
1. a method for separated inanimate matter from coal directly-liquefied residue, comprises the following steps in order:
1) pulverize and/or grind coal directly-liquefied residue, obtaining the fine powder that particle diameter is less than 100 microns;
2) above-mentioned fine powder is mixed mutually with solvent I, under whipped state, in 20～300 ℃, react 0.5～20 hour, the weight ratio of the fine powder of described solvent I and coal directly-liquefied residue is 1:1～20:1, and described solvent I comprises that concentration is 1～40(weight) mineral acid of %;
3) reaction product of step (2) is filtered and/or the centrifugal filter cake I that obtains;
4) above-mentioned filter cake I is mixed mutually with solvent II, under whipped state, in 20～300 ℃ of reactions 0.5～20 hour, the weight ratio of described solvent II and filter cake I is 1:1～20:1, described solvent II comprised that concentration is 1～60(weight) mineral alkali of %;
5) reaction product of step (4) is filtered and/or the centrifugal filter cake II that obtains, then filter cake II is dried;
6) optionally, step (2) to step (5) is repeated 1～5 time.
2. method according to claim 1, wherein said solvent I and/or solvent II also comprise 0.1～10(weight) tensio-active agent and/or the 0.1～10(weight of %) alcohol of %.
3. method according to claim 1 is wherein carried out the operation of step (2) and/or step (4) under the condition of pressurization, negative pressure, normal pressure or change pressure.
4. method according to claim 1, wherein in the reaction process of step (2) and/or step (4), the organic matter in coal directly-liquefied residue exists with liquid state or solid-state form.
5. method according to claim 1, the mineral acid in wherein said solvent I is selected from hydrochloric acid, fluoric acid, silicofluoric acid, sulfuric acid, nitric acid, industrial waste acid and their mixture.
6. method according to claim 1, the mineral alkali in wherein said solvent II is sodium hydroxide, ammoniacal liquor, industrial alkali waste and/or their mixture.
7. method according to claim 2, wherein said tensio-active agent is selected from cats product, anion surfactant, nonionogenic tenside and their mixture.
8. method according to claim 2, wherein said alcohol is selected from methyl alcohol, ethanol, propyl alcohol and their mixture.
9. method according to claim 1, wherein, reclaims the transition metal in the filtrate obtaining in step (3) and/or in the filtrate obtaining in step (5) by redox reaction.
10. method according to claim 1, wherein further carries out rectifying or extraction treatment with extraction agent by the filter cake II obtaining in step (5), so that the asphaltene in coal directly-liquefied residue, preasphaltene and/or mink cell focus is completely separated with inanimate matter.
11. methods according to claim 10, wherein said extraction agent comprises ionic liquid and/or organic solvent.
12. methods according to claim 1, wherein the filter cake II obtaining in step (5) is further melted to mixed processing with the molten mixture of at least two kinds of polycomponent aromatic hydrocarbons containing the aromatic hydroxy compound of 2-5 aromatic nucleus, organic matter in filter cake II is completely separated with inanimate matter, to obtain mesophase pitch.
13. methods according to claim 1, the direct liquefaction residue after the removal inanimate matter that wherein said method obtains can be used for making mesophase pitch matter, through polymerization, spinning and carburising step, is used to manufacture carbon fiber.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232135A (en) * | 2014-09-25 | 2014-12-24 | 四川创越炭材料有限公司 | Purification method for coal pitch with high softening point |
| CN104774635A (en) * | 2015-03-27 | 2015-07-15 | 陕西省石油化工研究设计院 | Treatment method for acid washing and deashing of coal liquefaction residue |
| CN109154108A (en) * | 2016-05-19 | 2019-01-04 | 株式会社神户制钢所 | Manufacturing method, carbon fiber and the electric double layer capacitor pole of carbon fiber |
| CN115385617A (en) * | 2022-08-12 | 2022-11-25 | 金陵科技学院 | High-performance concrete and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020011427A1 (en) * | 2000-06-13 | 2002-01-31 | Romine H. Ernest | Solvating component and solvent system for mesophase pitch |
| CN101885976A (en) * | 2010-07-02 | 2010-11-17 | 神华集团有限责任公司 | Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof |
| CN102153081A (en) * | 2011-04-28 | 2011-08-17 | 神华集团有限责任公司 | Method for preparing activated carbon by utilizing direct coal liquefaction residue |
-
2012
- 2012-06-25 CN CN201210215707.5A patent/CN103509576B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020011427A1 (en) * | 2000-06-13 | 2002-01-31 | Romine H. Ernest | Solvating component and solvent system for mesophase pitch |
| CN101885976A (en) * | 2010-07-02 | 2010-11-17 | 神华集团有限责任公司 | Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof |
| CN102153081A (en) * | 2011-04-28 | 2011-08-17 | 神华集团有限责任公司 | Method for preparing activated carbon by utilizing direct coal liquefaction residue |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232135A (en) * | 2014-09-25 | 2014-12-24 | 四川创越炭材料有限公司 | Purification method for coal pitch with high softening point |
| CN104774635A (en) * | 2015-03-27 | 2015-07-15 | 陕西省石油化工研究设计院 | Treatment method for acid washing and deashing of coal liquefaction residue |
| CN109154108A (en) * | 2016-05-19 | 2019-01-04 | 株式会社神户制钢所 | Manufacturing method, carbon fiber and the electric double layer capacitor pole of carbon fiber |
| CN115385617A (en) * | 2022-08-12 | 2022-11-25 | 金陵科技学院 | High-performance concrete and preparation method thereof |
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