CN103509576B - 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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- CN103509576B CN103509576B CN201210215707.5A CN201210215707A CN103509576B CN 103509576 B CN103509576 B CN 103509576B CN 201210215707 A CN201210215707 A CN 201210215707A CN 103509576 B CN103509576 B CN 103509576B
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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 50
- 239000000126 substance Substances 0.000 title abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 60
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 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
- 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
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001035 drying 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 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000010426 asphalt Substances 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
- 239000000835 fiber Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000000746 purification Methods 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
- 230000009467 reduction Effects 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 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
- 230000001172 regenerating effect Effects 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
- 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
- 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
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 method being separated inanimate matter from coal directly-liquefied residue, particularly relate to the method obtaining the mesophase pitch matter for the preparation of carbon fiber after being separated inanimate matter by described method from coal directly-liquefied residue.
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 accounting for raw coal total amount 20 ~ 30%.Effectively utilize these liquefied residues, have immeasurable impact to the resource utilization of direct coal liquefaction process and economy.
For many years, both at home and abroad all constantly exploring the method utilizing coal directly-liquefied residue (DCLR), at present, the method for coal directly-liquefied residue is utilized mainly to comprise: by liquefied residue vaporizing system for synthetic gas; Liquefied residue is carried out 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, regenerative ratio carbon fibre material etc.Particularly, in recent years, separate bitumen alkene and preasphaltene from coal directly-liquefied residue, modifiedly prepare mesophase pitch, regenerative ratio carbon fiber, the study hotspot that coal directly-liquefied residue utilizes, general method separate bitumen alkene and the preasphaltene from coal directly-liquefied residue adopting extraction.
But, 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 thoroughly constitute 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 separate bitumen alkene and preasphaltene process in improve operation easier, add process costs.Such as, CN101885976, CN101580729A, CN1948148A, CN1629257A, CN101962560A and CN101962561A disclose the technique 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 used 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.Be separated the asphaltene, preasphaltene and/or the mink cell focus that obtain with described extraction agent and can prepare mesophase pitch through a step again by heating destructive distillation, and then produce carbon fibre material.
In the method using extraction agent separate bitumen alkene and preasphaltene from coal directly-liquefied residue, because the softening temperature of coal directly-liquefied residue is relatively high, general employing high-temperature operation and/or high top pressure operation are mixed in extraction agent by molten for coal directly-liquefied residue, 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 discloses a kind of solvent composition for dissolving mesophase pitch, this composition comprises aromatic hydrocarbons mixture, its atmospheric boiling point is approximately 285-500 DEG C, preferably at least 80% carbon atom is aromatize, such aromatic hydroxy compound example comprises containing the aromatic hydroxy compound of 2-5 aromatic nucleus and the aromatic hydroxy compound containing the replacement of 2-5 aromatic nucleus, hydrogenation or replacement hydrogenation, wherein substituting group is the alkyl with 1-3 carbon atom, such as in the wrong, dibenzphenanthrene, 5,6-dihydro are bent, 1,7-dimethyl is bent, 1-methyl, 5,6-dihydro is bent etc.This solvent composition can be used for the mesophase pitch diluting high molecular, to make its viscosity, yield temperature and melt temperature reduce, thus when preparing carbon fiber with it, is conducive to adopting lower temperature to carry out spinning operation.
Although above-mentioned molten mixing method eliminates necessary later separation step in the method using extraction agent separate bitumen alkene, but because the asphaltene of inanimate matter easily with a large amount of of high-content in coal directly-liquefied residue is bonding, the easy blocking filtering device when filter operation, need higher working pressure, and inevitable loss part bituminous matter.
All disclosures of above-mentioned patent documentation are introduced with for referencial use in full at this.
For solving institute's problems faced in above-mentioned prior art, the chemical deliming method being mainly used in coal washing industry is introduced in this area by the present inventor, 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 the difficulty being therefore separated inanimate matter is larger.The present invention with acid-soluble dose with the catalyzer in 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, reduce the interference of inanimate matter, thus improve the use value of coal directly-liquefied residue.Further, the present inventor by adding certain density tensio-active agent and/or alcohol in acid-soluble dose and/or alkali solvent, improve acid-soluble dose or alkali solvent to the wetting property of coal directly-liquefied residue, also improve the efficiency of whole sepn process simultaneously, promptly make to be separated with pickle solution and/or alkaline wash containing organic reaction product after pickling and/or alkali cleaning, significantly improve separating effect, reduce separation costs.Importantly, eliminate most of inanimate matter from coal directly-liquefied residue after, by extraction process or when melting mixed method separate bitumen alkene and preasphaltene, service temperature and/or working pressure can be reduced, thus decrease running cost, and more valuable carbon fiber precursor can be extracted.In addition, because some valuable transition metal being contained in coal directly-liquefied residue, the reaction solution that also can obtain from coal directly-liquefied residue and acid-soluble dose and alkali solvent reaction if desired, transition metal is reclaimed.
Summary of the invention
As previously mentioned, for overcoming above-mentioned prior art problem, the invention provides a kind of method being separated inanimate matter from coal directly-liquefied residue, comprising 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, in 20 ~ 300 DEG C of reactions 0.5 ~ 20 hour under whipped state, described solvent I is 1:1 ~ 20:1 with the weight ratio of the fine powder of coal directly-liquefied residue, and it is 1 ~ 40(weight that described solvent I comprises concentration) mineral acid of %;
3) reaction product of step (2) filtered and/or centrifugally obtain filter cake I;
4) mixed mutually with solvent II by above-mentioned filter cake I, in 20 ~ 300 DEG C of reactions 0.5 ~ 20 hour under whipped state, described solvent II is 1:1 ~ 20:1 with the weight ratio of filter cake I, and it is 1 ~ 60(weight that described solvent II comprises concentration) mineral alkali of %;
5) reaction product of step (4) filtered and/or centrifugally obtain filter cake II, then filter cake II being dried;
6) optionally, step (2) is repeated 1 ~ 5 time to step (5).
For improving acid-soluble dose or alkali solvent to the wetting property of direct liquefaction residue and the separating effect improving pickle solution or alkaline wash and reaction product, described solvent I and/or solvent II also can comprise 0.1 ~ 10(weight) tensio-active agent of % and/or 0.1 ~ 10(weight) 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) can carry out under pressurization, negative pressure, normal pressure or the condition changing pressure.And the organic matter in the reaction process of step (2) and/or step (4) in coal directly-liquefied residue exists with liquid or solid-state form.
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 the 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 obtained in the filtrate obtained in step (3) and/or in step (5) is reclaimed by redox reaction.
On the basis of the method in the present invention first, the filter cake II obtained in step (5) is carried out rectifying or extraction treatment with extraction agent further, the asphaltene in coal directly-liquefied residue, preasphaltene and/or mink cell focus to be separated completely 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 first, the filter cake II obtained in step (5) is melted mixture with at least two kinds of polycomponent aromatic hydrocarbons containing the aromatic hydroxy compound of 2-5 aromatic nucleus further and carries out molten mixed process, organic matter in filter cake II is separated completely with inanimate matter, to obtain mesophase pitch.
Can be used for obtained mesophase pitch matter according to the direct liquefaction residue after the removal inanimate matter that the method for separation inanimate matter of the present invention obtains, through polymerization, spinning and carburising step, be used to manufacture carbon fiber.
Accompanying drawing explanation
Fig. 1 adds Sodium dodecylbenzene sulfonate (LAS) the distributed effect figure of coal directly-liquefied residue in acid-soluble dose before in acid-soluble dose of the embodiment of the present invention 2.
Fig. 2 is with the distributed effect figure of reaction product in pickle solution after the sour solvent treatment adding Sodium dodecylbenzene sulfonate (LAS) in the embodiment of the present invention 2.
Fig. 3 be add ethanol in the alkali solvent of the embodiment of the present invention 3 before the distributed effect figure of coal directly-liquefied residue in alkali solvent.
Fig. 4 is with the distributed effect figure of reaction product in alkaline wash after the alkali solvent treatment adding ethanol in the embodiment of the present invention 3.
Embodiment
The present invention is further explained in detail by the description below with reference to accompanying drawing, but below describe only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.
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 the 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 existed in coal directly-liquefied residue is condensed aromatic hydrocarbon, it is characterized in that C/H atomic ratio is high.Such aromatic hydrocarbon or anine, because of limited durability, when for the preparation of carbon fiber, are estimated before being spun into fiber, can be polymerized under mild conditions.But before being used to prepare carbon fiber, the purity of above-mentioned aromatic hydrocarbon resin must be ensured.This proposes high requirement to separation or extraction process.
In the present invention, the solvent of coal directly-liquefied residue containing acid or alkali is processed successively, above-mentioned inanimate matter is wherein dissolved in described solvent, reaches the effect that the organic matter in coal directly-liquefied residue is effectively separated with inanimate matter.From coal directly-liquefied residue, be separated the process of inanimate matter, comprise following step in order:
The first step: coal directly-liquefied residue is pulverized and/or grinding, obtains 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: mixed mutually with solvent I by above-mentioned fine powder, it is 1 ~ 40(weight that described solvent I comprises concentration) 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 filtered and/or centrifugally obtain filter cake I;
3rd step: mixed mutually with solvent II by above-mentioned filter cake I, it is 1 ~ 60(weight that described solvent II comprises concentration) 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 centrifugally obtains filter cake II, filter cake II is dried.
In fact, according to actual requirement, second step and the 3rd step can be repeated 1 ~ 5 time.Service temperature in second step and the 3rd step is 20 ~ 300 DEG C, and the reaction times is 0.5 ~ 20 hour.And the pressure that the 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, the pressure changed is selected to be say can select different pressure conditions in second step or the 3rd step, such as, after first negative pressure normal pressure, also can select the mode of interim change pressure simultaneously or progressively change the mode of pressure.
In addition, for improving acid-soluble dose or alkali solvent to the wetting property of coal directly-liquefied residue and the separating effect improving pickle solution or alkaline wash and reaction product, described solvent I and/or solvent II also can comprise 0.1 ~ 10(weight) tensio-active agent of % and/or 0.1 ~ 10(weight) 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, after being separated the most of inanimate matter of removal by above-mentioned steps from coal directly-liquefied residue, by filter cake II extraction agent is carried out rectifying or extraction treatment further, reach asphaltene, preasphaltene and/or mink cell focus and be separated completely with inanimate matter; Or, after being separated the most of inanimate matter of removal by above-mentioned steps from coal directly-liquefied residue, also carry out molten mixed process by filter cake II is melted mixture with at least two kinds of polycomponent aromatic hydrocarbons containing the aromatic hydroxy compound of 2-5 aromatic nucleus further, reach organic and be separated completely with inanimate matter.
With acid-soluble dose with the catalyzer in 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, thus the inanimate matter in coal directly-liquefied residue and organic bondability is greatly reduced, reduce the interference of inanimate matter, thus operational condition when making follow-up rectifying, extraction or melt mixed process will be no longer harsh, the operating time also will shorten greatly.Further, by adding certain density tensio-active agent and/or alcohol in acid-soluble dose and/or alkali solvent, improve acid-soluble dose or alkali solvent to the wetting property of coal directly-liquefied residue, also improve the efficiency of whole sepn process simultaneously, promptly make to be separated with pickle solution and/or alkaline wash containing organic reaction product after pickling and/or alkali cleaning, significantly improve separating effect, reduce separation costs.Importantly, eliminate most of inanimate matter from coal directly-liquefied residue after, by extraction process or when melting mixed method separate bitumen alkene and preasphaltene, service temperature and/or working pressure can be reduced, thus decrease running cost, and more valuable carbon fiber precursor can be extracted.In addition, because some valuable transition metal being contained in coal directly-liquefied residue, the reaction solution that also can obtain from coal directly-liquefied residue and acid-soluble dose and alkali solvent reaction if desired, transition metal is reclaimed.
Embodiment
Further describe the present invention by detailed one exemplary embodiment below, but these embodiments do not form any limitation of the invention.
Embodiment 1
Carry out the test of embodiment 1 according to the following steps:
1) coal directly-liquefied residue is pulverized and grinding, obtain the fine powder that particle diameter is 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, stirring reaction 10 hours under normal pressure, the condition of 23 DEG C, is then washed, suction filtration is obtained filter cake I;
3) filter cake I of 17.1g is added in the NaOH solvent (concentration is 34%) of 100g, stirring reaction 1.5 hours under normal pressure, the condition of 90 DEG C, then washed, suction filtration obtains filter cake II.
4) dried by filter cake II, analyze the weight percent content of its inanimate matter and C/H ratio, result is as shown in table 1.
Table 1
| Before process | 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% |
Can find out from the testing data of table 1 above: 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 based on aromatic hydrocarbon.
Embodiment 2
Carry out the test of embodiment 2 according to the following steps:
1) coal directly-liquefied residue is pulverized and grinding, obtain the fine powder that particle diameter is 10 microns;
2) the above-mentioned fine powder of 20g is added in the hydrochloric acid soln (concentration is 36%) of 100g, the distributed effect of coal directly-liquefied residue in acid-soluble dose is shown in Fig. 1, then add Sodium dodecylbenzene sulfonate tensio-active agent (LAS, concentration is 4%), under normal pressure, the condition of 30 DEG C, stirring reaction left standstill after 5 hours, now the distributed effect of coal directly-liquefied residue in pickle solution is shown in Fig. 2, organic phase is separated with pickle solution, carries out suction filtration and obtains filter cake I;
3) filter cake I of 15.9g is added in the NaOH solvent (concentration is 34%) of 100g, stirring reaction 1.5 hours under normal pressure, the condition of 90 DEG C, then washed, suction filtration obtains filter cake II.
4) dried by filter cake II, analyze the weight percent content of its inanimate matter, result is as shown in table 2.
Table 2
| Before process | After acid treatment | After alkaline purification | Reduction | |
| Inanimate matter, % by weight | 26.1 5 | 6.62 | 5.81 | 82.6% |
Can find out from the testing data and Fig. 1 and Fig. 2 of table 2 above: after the sour solvent treatment adding 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 obviously, are conducive to carrying out separating treatment in step (2).
Embodiment 3
Carry out the test of embodiment 3 according to the following steps:
1) coal directly-liquefied residue is pulverized and grinding, obtain the fine powder that particle diameter is 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, stirring reaction 10 hours under normal pressure, the condition of 23 DEG C, is then washed, suction filtration is obtained filter cake I;
3) filter cake I of 17.2g is added in the NaOH solvent (concentration is 34%) of 100g, coal directly-liquefied residue is shown in Fig. 3 at the distributed effect in alkali solvent, then add the ethanol (concentration is 50%) of 10g, under normal pressure, the condition of 20 DEG C, stirring reaction left standstill after 5 hours, now the distributed effect of coal directly-liquefied residue in alkaline wash is shown in Fig. 4, organic phase is separated with alkaline wash, suction filtration obtains filter cake II.
4) dried by filter cake II, analyze the weight percent content of its inanimate matter, result is as shown in table 3.
Table 3
| Before process | After acid treatment | After alkaline purification | Reduction | |
| Inanimate matter, % by weight | 26.1 5 | 9.1 | 6.22 | 81.3% |
Can find out from the testing data and Fig. 3 and Fig. 4 of table 3 above: in alkali solvent, add ethanol contribute to removing inanimate matter from coal directly-liquefied residue, simultaneously, after the alkali solvent treatment adding ethanol, in alkaline wash, organic phase and inorganic phase layering obviously, are conducive to carrying 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, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its integral part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary; those skilled in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (13)
1. from coal directly-liquefied residue, be separated a method for 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, in 20 ~ 300 DEG C of reactions 0.5 ~ 20 hour under whipped state, described solvent I is 1:1 ~ 20:1 with the weight ratio of the fine powder of coal directly-liquefied residue, and described solvent I comprises the mineral acid that concentration is 1 ~ 40 % by weight;
3) reaction product of step (2) filtered and/or centrifugally obtain filter cake I;
4) mixed mutually with solvent II by above-mentioned filter cake I, in 20 ~ 300 DEG C of reactions 0.5 ~ 20 hour under whipped state, described solvent II is 1:1 ~ 20:1 with the weight ratio of filter cake I, and described solvent II comprises the mineral alkali that concentration is 1 ~ 60 % by weight;
5) reaction product of step (4) filtered and/or centrifugally obtain filter cake II, then filter cake II being dried;
6) optionally, step (2) is repeated 1 ~ 5 time to step (5).
2. method according to claim 1, wherein said solvent I and/or solvent II also comprise the tensio-active agent of 0.1 ~ 10 % by weight and/or the alcohol of 0.1 ~ 10 % by weight.
3. method according to claim 1, wherein pressurization, negative pressure, normal pressure or change pressure condition under carry out the operation of step (2) and/or step (4).
4. method according to claim 1, the organic matter wherein in the reaction process of step (2) and/or step (4) in coal directly-liquefied residue exists with liquid 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, is reclaimed the transition metal in the filtrate obtained in the filtrate obtained in step (3) and/or in step (5) by redox reaction.
10. method according to claim 1, wherein the filter cake II obtained in step (5) is carried out rectifying or extraction treatment with extraction agent further, the asphaltene in coal directly-liquefied residue, preasphaltene and/or mink cell focus to be separated completely 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 obtained in step (5) is melted mixture with at least two kinds of polycomponent aromatic hydrocarbons containing the aromatic hydroxy compound of 2-5 aromatic nucleus further and carry out molten mixed process, organic matter in filter cake II is separated completely 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 obtained mesophase pitch matter, through polymerization, spinning and carburising step, is used to manufacture carbon fiber.
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| 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 |
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