CN104845662A - A method for extracting phenolic compounds in coal liquefaction oil - Google Patents
A method for extracting phenolic compounds in coal liquefaction oil Download PDFInfo
- Publication number
- CN104845662A CN104845662A CN201510202567.1A CN201510202567A CN104845662A CN 104845662 A CN104845662 A CN 104845662A CN 201510202567 A CN201510202567 A CN 201510202567A CN 104845662 A CN104845662 A CN 104845662A
- Authority
- CN
- China
- Prior art keywords
- aqueous phase
- phase solution
- solution
- extracting method
- phenolic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002989 phenols Chemical class 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 79
- 239000003245 coal Substances 0.000 title claims abstract description 57
- 239000008346 aqueous phase Substances 0.000 claims abstract description 113
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims description 187
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 48
- 239000012071 phase Substances 0.000 claims description 44
- 239000012266 salt solution Substances 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 159000000011 group IA salts Chemical class 0.000 claims description 29
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 17
- 235000011089 carbon dioxide Nutrition 0.000 claims description 17
- 150000001447 alkali salts Chemical class 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 abstract description 37
- 239000002253 acid Substances 0.000 abstract description 23
- 239000002699 waste material Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 2
- 239000010808 liquid waste Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 52
- 238000011084 recovery Methods 0.000 description 42
- 239000002994 raw material Substances 0.000 description 11
- 238000013517 stratification Methods 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003822 preparative gas chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- -1 chemical method Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for extracting phenolic compounds in coal liquefaction oil. The extraction method comprises the following steps: the step S1) mixing the coal liquefaction oil and an alkaline saline solution to form a first mixture solution; the step S2) separating aqueous phase of the first mixture solution to obtain a first aqueous phase solution; and the step S3) adjusting the pH value of the first aqueous phase solution to be lower than 6.0 to obtain a second aqueous phase solution comprising the phenolic compounds. According to the extraction method, the phenolic compounds in the coal liquefaction oil can be extracted only adopting the strong-alkaline and weak-acid alkaline saline solution, so that the problem of severe corrosion on extraction equipment caused by adopting strong alkali or strong acid to extract the phenolic compounds in the coal liquefaction oil in the prior art is overcome; and meanwhile, the waste generated in the method is easy to recycle, thereby preventing the problem that it is hard to recycle liquid waste generated when adopting the strong alkali or strong acid to extract the phenolic compounds in the coal liquefaction, and preventing pollution to the environment.
Description
Technical field
The present invention relates to coal liquifaction chemical field, the extracting method of phenolic compound in a kind of liquefied coal coil.
Background technology
Coal is the fossil resource of non-renewable preciousness, and as energy utilization, coal facilitates the development of first and second Industrial Revolution, lays a good foundation for modern social economy increases.Especially in China, coal role in national economy is more obvious.Gelatin liquefaction technology is at China's comparative maturity, and it, mainly the coal of solid state direct and hydrogen reaction under high pressure and certain temperature, makes coal directly change into the Technology of the usual alleged liquefied coal coil of liquid oil and this area.Although the concrete composition difference to some extent of the liquefied coal coil that different coal liquefaction crafts obtains, wherein all containing more oxygenatedchemicals, wherein major part is phenolic compound, generally can reach 14%-16%.
On the one hand, the existence of these phenolic compounds, the hydrogenation process follow-up to liquefied coal coil can bring a lot of problem, and the hydrogen consumption of hydrogenation process not only can be made to increase, and the water that its reaction generates simultaneously will produce also adverse influence to catalyst activity and life-span.On the other hand, the application of phenolic compound is comparatively extensive, and it is the raw material of a lot of chemical industry, is also the intermediate of the products such as medicine, agricultural chemicals, spices, pigment, softening agent, antioxidant, has high Economic Value Added.Therefore, the Technology of phenolic compound is extracted in exploitation from liquefied coal coil, is separated by these phenolic compounds and produces phenols chemical, not only can widen the utilization ways of liquefied coal coil, the hydrogen consumption of follow-up hydrogenation process and the severity of processing condition can also be reduced, improve economy.
According to chemistry and the physical property of phenolic compound, there is now the method for multiple extraction phenolic compound, mainly chemical method, selective solvent method, supercritical extraction and pressure crystallization.But above-mentioned various method all exists certain defect, make a concrete analysis of as follows.
Publication number be US4256568A and US4595489A U.S. patent applications disclose the chemical method utilizing sodium hydroxide solution extraction phenols, this method is more ripe, less containing neutral oil in the phenols extracted, extraction effect is more excellent, but the method is owing to using strong acid and highly basic in reaction, comparatively large to equipment corrosion, and the waste generated is difficult to reclaim, and can produce more serious environmental pollution.
Publication number US2790834A, US2888491A, US4275246A, US20040200717A1 and US2005240065A1 U.S. patent applications discloses selective solvent method, this method utilizes the solubleness of some solvent to phenolic compound higher, and the principle very low to the solubleness of oily substance is extracted the phenolic compound in liquefied coal coil, solvent in this method is generally unit alcohol or polyvalent alcohol, such as methyl alcohol, ethanol, ethylene glycol or glycerine, this method also comparative maturity, but its maximum drawback is in the phenols extracted containing more neutral oil, although the lower recovery of unit alcohols price is also easier to simultaneously, but it is poor to the selective dissolution ability of phenolic compound, layering is comparatively difficult, and the selectivity of polyvalent alcohol extraction is poor, neutral oil is carried secretly even more serious.
Publication number be US4827050SA U.S. patent applications disclose supercritical extraction, although the leaching process of this method is simple, be still in theoretical research stage at present, practice system is still incomplete.The publication number pressure crystallization that has been the Japanese Patent Application Publication of JP1213246A, this method is also in the laboratory study stage, and the huge shortage application possibility of facility investment.
Along with the environmental requirement that Coal Chemical Industry is fast-developing and day by day harsh, need a kind of phenols extracting method avoiding using strong acid and strong base.
Summary of the invention
Main purpose of the present invention is the extracting method providing phenolic compound in a kind of liquefied coal coil, to solve the extraction problem that strong acid and strong base can only be used to carry out phenols of the prior art.
To achieve these goals, according to an aspect of the present invention, provide the extracting method of phenolic compound in a kind of liquefied coal coil, this extracting method comprises: step S1, and liquefied coal coil and alkaline salt solution are mixed to form the first mixing solutions; Step S2, is separated the aqueous phase of above-mentioned first mixing solutions, obtains the first aqueous phase solution; And step S3, the pH value of above-mentioned first aqueous phase solution is adjusted to and is less than 6.0, obtain the second aqueous phase solution containing phenolic compound.
Further, the weight ratio of above-mentioned alkaline salt solution and liquefied coal coil is 1:2 ~ 6:2.
Further, the mass concentration of above-mentioned alkaline salt solution is 5% ~ 30%, and preferred above-mentioned alkaline salt solution is sodium carbonate, S-WAT or salt of wormwood.
Further, above-mentioned steps S1 adopts the stirring velocity of 60r/min ~ 180r/min to stir 5 ~ 60min and obtains above-mentioned first mixing solutions, and the envrionment temperature of preferred above-mentioned stirring is 20 DEG C ~ 80 DEG C.
Further, above-mentioned steps S2 comprises: leave standstill aqueous phase and oil phase that above-mentioned mixing solutions obtains layering, isolate above-mentioned aqueous phase and obtain above-mentioned first aqueous phase solution, the above-mentioned standing time is 5 ~ 60min.
Further, above-mentioned steps S3 adopt in above-mentioned first aqueous phase solution, pass into carbonic acid gas method by the pH regulator of above-mentioned first aqueous phase solution to being less than 6.0.
Further, above-mentioned steps S3 adopt in above-mentioned first aqueous phase solution, pass into carbonic acid gas method by the pH regulator of above-mentioned first aqueous phase solution to being less than 6.0.
Further, step S4, mixes above-mentioned second aqueous phase solution with organic solvent, obtains the organic phase solution containing above-mentioned phenolic compound.
Further, above-mentioned steps S4 comprises: step S41, and above-mentioned second aqueous phase solution is cooled to 15 ~ 20 DEG C; Step S42, mixes above-mentioned second aqueous phase solution with above-mentioned organic solvent, obtains the second mixing solutions; And step S43, leave standstill above-mentioned second mixing solutions, be separated and obtain organic phase solution and the 3rd aqueous phase solution, the above-mentioned standing time is 5 ~ 60min.
Further, the volume ratio of above-mentioned organic solution and above-mentioned second aqueous phase solution is between 1:3 ~ 1:1.
Further, above-mentioned organic solvent is methylene dichloride and/or octanol.
Further, above-mentioned steps S42 adopts the stirring velocity of 60r/min ~ 180r/min to stir 5 ~ 20min and obtains above-mentioned second mixing solutions.
Further, above-mentioned steps S43 also comprises: step a, carries out drying, obtain enriched material to above-mentioned 3rd aqueous phase solution; With; Step b, heats above-mentioned enriched material, obtains basic salt and carbonic acid gas.
Further, above-mentioned basic salt returns above-mentioned steps S1 recycling, and above-mentioned carbonic acid gas returns above-mentioned steps S3 for regulating the pH value of above-mentioned first aqueous phase solution.
Apply technical scheme of the present invention, only the alkaline salt solution of strong base weak acid need be adopted just the phenolic compound in liquefied coal coil can be extracted, overcome in prior art and adopt phenolic compound in highly basic or strong acid extraction liquefied coal coil to the heavy corrosion of extraction equipment; Meanwhile, the waste of the generation of present method is easier to reclaim, and it also avoid the difficult problem reclaimed of waste liquid generated when adopting strong acid or highly basic to extract, and then avoids the pollution to environment.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic flow sheet of the extracting method of phenolic compound in the liquefied coal coil in a kind of exemplary embodiments.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
In the typical embodiment of the one of the application, provide the extracting method of phenolic compound in a kind of liquefied coal coil, as shown in Figure 1, this extracting method comprises: step S1, and liquefied coal coil and alkaline salt solution are mixed to form the first mixing solutions; Step S2, is separated the aqueous phase of above-mentioned first mixing solutions, obtains the first aqueous phase solution; And step S3, the pH value of above-mentioned first aqueous phase solution is adjusted to and is less than 6.0, obtain the second aqueous phase solution containing phenolic compound.
In above-mentioned extracting method, first liquefied coal coil and alkaline salt solution are mixed to form the first mixing solutions, phenolic compound has slightly acidic, can react with the alkaline salt solution of strong base weak acid, phenolic compound is transferred in aqueous phase from liquefied coal coil, and the hydrocarbons in liquefied coal coil can not react with alkaline salt solution, so adopt the phenolic compound in strong base-weak acid salt solution separating liquefied coal coil to have good selectivity and higher resolution; Then, be separated the aqueous phase of above-mentioned first mixing solutions, obtain the first aqueous phase solution, the first aqueous phase solution comprises basic salt and phenates, and does not comprise the hydrocarbons in liquefied coal coil, the phenolic compound in liquefied coal coil and hydrocarbons is separated like this; Finally the pH value of above-mentioned first aqueous phase solution is adjusted to and is less than 6.0, make solution be acid, neutralize the second aqueous phase solution that the basic salt of the first aqueous phase solution and phenates obtain containing phenolic compound again.
Above-mentioned extracting method, only the alkaline salt solution of strong base weak acid need be adopted just the phenolic compound in liquefied coal coil can be extracted, overcome in prior art and adopt phenolic compound in highly basic or strong acid extraction liquefied coal coil to the heavy corrosion of extraction equipment; Meanwhile, the waste of the generation of present method is easier to reclaim, and it also avoid the difficult problem reclaimed of waste liquid generated when adopting strong acid or highly basic to extract, and then avoids the pollution to environment.
In a kind of preferred embodiment of the application, the weight ratio of above-mentioned alkaline salt solution and liquefied coal coil is 1:2 ~ 6:2, and such weight ratio makes the two fully to react, and then the phenolic compound of the overwhelming majority in liquefied coal coil can be extracted.Obtain higher extraction yield.Wherein, the alkaline salt solution that can be used for the application includes but not limited to that preferred above-mentioned alkaline salt solution is sodium carbonate, S-WAT or salt of wormwood.
In order to ensure that phenolic compound and basic salt fully react, and then from liquefied coal coil, extract more phenolic compound, avoid basic salt quantity not sufficient and cause phenolic compound can not the problem of sufficient reacting, and then the extraction yield improving phenolic compound avoids again the use of too much water resources, the mass concentration of preferred alkaline salt solution is 5% ~ 30%.
In the another kind of preferred embodiment of the application, the stirring velocity of 60r/min ~ 180r/min that adopts preferred above-mentioned steps S1 stirs 5 ~ 60min and obtains above-mentioned first mixing solutions, phenolic compound can be made so fully to contact with basic cpd, and improve the speed of reaction of the two.In order to improve the speed of reaction of phenolic compound and basic salt further, in the reaction times of both shortenings, improve extraction efficiency, in the further preferably above-mentioned steps S1 of the application, the envrionment temperature of above-mentioned stirring is 20 DEG C ~ 70 DEG C.
Fully react to make phenolic compound and alkaline salt solution, make more phenolic compound change phenates into be dissolved in the water, and then extract more phenolic compound, improve the extraction yield of phenolic compound, the preferred above-mentioned steps S2 of the application comprises: leave standstill aqueous phase and oil phase that above-mentioned mixing solutions obtains layering, isolate above-mentioned aqueous phase and obtain the first aqueous phase solution, the preferred above-mentioned standing time is 5 ~ 60min.
In addition, in order to reduce the cost of the method, low-carbon environment-friendly, convenient recycling, preferred above-mentioned steps S3 adopt in above-mentioned first aqueous phase solution, pass into carbonic acid gas method by the pH regulator of above-mentioned first aqueous phase solution to being less than 6.0.
In another preferred embodiment of the application, said extracted method also comprises after above-mentioned steps S3: step S4, is mixed by above-mentioned second aqueous phase solution, obtain the organic phase solution containing above-mentioned phenolic compound with organic solvent.Phenolic compound in organic solvent solubleness is far longer than the solubleness in water, the phenolic compound of the overwhelming majority will can be transferred in organic phase solvent so above-mentioned second aqueous phase solution is mixed with organic solvent, and be conducive to the follow-up extraction processing of phenolic compound and analyze.
In order to improve the extraction yield of phenolic compound, preferred above-mentioned steps S4 comprises: step S41, and above-mentioned second aqueous phase solution is cooled to 15 ~ 20 DEG C; Step S42, mixes above-mentioned second aqueous phase solution with above-mentioned organic solvent, obtains the second mixing solutions; And step S43, leave standstill above-mentioned second mixing solutions, be separated and obtain organic phase solution and the 3rd aqueous phase solution, the preferred above-mentioned standing time is 5 ~ 60min.Because the reaction of alkaline salt solution and phenolic compound can release certain heat, make the temperature of the second aqueous phase solution higher, and higher temperature is unfavorable for the separation of system, therefore before above-mentioned second aqueous phase solution mixes with above-mentioned organic solvent, above-mentioned second aqueous phase solution is cooled to 15 ~ 20 DEG C, to the separation of system be conducive to, more phenolic compound is transferred in organic solvent, and then improve the extraction yield of phenolic compound.After above-mentioned second aqueous phase solution mixes with above-mentioned organic solvent, leave standstill above-mentioned second mixing solutions 5 ~ 60min, further ensure more phenolic compound and transfer in organic solvent, improve the extraction yield of phenolic compound further.
In order to make the most of phenolic compound in the second aqueous phase solution as much as possible all transfer in organic solvent, the volume ratio of the preferred above-mentioned organic solution of the application and above-mentioned second aqueous phase solution is between 1:3 ~ 1:1.
In another preferred embodiment of the application, above-mentioned organic solvent is methylene dichloride and/or octanol, the solubleness of phenolic compound in methylene dichloride and octanol organic solvent is comparatively large, can ensure that the most of phenolic compound in the second aqueous phase solution is all transferred in organic solvent so further.
In order to make phenolic compound fully dissolve in organic solvent, and make its rapid solution in organic solvent, the preferred above-mentioned steps S42 of the application adopts the stirring velocity of 60r/min ~ 180r/min to stir 5 ~ 20min and obtains above-mentioned second mixing solutions.
In another preferred embodiment of the application, above-mentioned steps S43 also comprises: step a, carries out drying, obtain enriched material to above-mentioned 3rd aqueous phase solution; And step b, heat above-mentioned enriched material, obtain basic salt and carbonic acid gas.Through such treatment step, can basic salt being isolated, when adopting carbonic acid gas to regulate the pH of above-mentioned first aqueous phase solution to when being less than 6.0 in step S3, after heating, also can isolate carbonic acid gas, the recycling of more convenient like this basic salt and carbonic acid gas, it also avoid the waste of resource.
In order to save the cost of the extracting method of the application, the preferred above-mentioned basic salt of the application returns above-mentioned steps S1 recycling, and above-mentioned carbonic acid gas returns above-mentioned steps S3 for regulating the pH value of above-mentioned first aqueous phase solution.
In another preferred embodiment of the application, the extraction progression of above-mentioned steps S1 and above-mentioned steps S4 is 1 ~ 5 grade.Extract the cost also can saving equipment while that progression can improving the extraction yield of phenolic compound within the scope of this.
In order to the technical scheme making those skilled in the art clearly understand the application, below in conjunction with embodiment and comparative example, the technical scheme to the application is described in detail.Wherein, P is the weight ratio of alkaline salt solution and liquefied coal coil, and Q is the mass concentration of alkaline salt solution.
Embodiment 1
To contain a certain amount of gelatin liquefaction flash oil 170 ~ 310 DEG C for raw material, total phenol content is wherein 7.30wt%.Get 40g raw material and be placed in separating funnel, add the sodium carbonate solution 60g that concentration is 25wt%, stratification 30min, be then separated and obtain the first aqueous phase solution and oil-phase solution.Improve one's methods with GB/T24207-2009 and measure the phenol content of oil-phase solution, obtain phenol content in oil-phase solution and drop to 0.52%.Pass into below carbonic acid gas adjust ph to 6.0 in first aqueous phase solution and obtain the second aqueous phase solution, second aqueous phase solution is cooled to 20 DEG C, add methylene dichloride, the volume ratio obtaining methylene dichloride and the second aqueous phase solution is second mixing solutions of 1:2, the organic phase solution and the 3rd aqueous phase solution that obtain enrichment phenolic compound is separated after second mixing solutions stratification 30min, because the phenolic compound in gelatin liquefaction flash oil is mainly phenol, so the large I of phenol recovery rate represents the size of the phenolic compound rate of recovery.The phenol recovery rate that the application adopts vapor-phase chromatography measurement to obtain is 94.94%, and in aqueous phase, the rear sodium carbonate rate of recovery is dried in solute dehydration is 87.79%.
Embodiment 2
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 3
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 4
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 5
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 6
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 7
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 8
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 9
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 10
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 11
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 12
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 13
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 14
Concrete operation method is identical with above-described embodiment, and operating parameters, in table 1, is separated the rate of recovery of phenol content, phenol in the oil-phase solution obtained after the extraction that records after obtaining the first aqueous phase solution and oil-phase solution and the sodium carbonate rate of recovery in table 2.
Embodiment 15
With phenol 11.23wt%, Witco 70 33.37wt% and naphthane 55.4wt% prepares that to simulate gelatin liquefaction slightly oily.Get 20g simulated oil and be placed in separating funnel, add concentration be 10wt% solution of potassium carbonate 40g mix and with the speed of 180r/min stir 30min, the envrionment temperature stirred is 30 DEG C, stratification 35min, is then separated and obtains the first aqueous phase solution and oil-phase solution.Improve one's methods with GB/T24207-2009 and measure the phenol content of oil-phase solution, obtain phenol content in oil-phase solution and drop to 2.24wt%.Below carbonic acid gas adjust ph to 6.0 is passed in first aqueous phase solution, methylene dichloride is added after being cooled to 20 DEG C, and stir 20min with the speed of 180r/min, the volume ratio of methylene dichloride and the second aqueous phase solution is 1:2, be separated the organic phase solution obtaining enrichment phenolic compound after stratification 30min, concrete operating parameters is in table 1.The rate of recovery adopting vapor-phase chromatography measurement to obtain phenol is 89.12%, and in aqueous phase, the rear sodium carbonate rate of recovery is dried in solute dehydration is 87.45%, and concrete test result is in table 2.
Embodiment 16
To contain a certain amount of gelatin liquefaction low point of oil 78 ~ 270 DEG C of components for raw material, total phenol content is wherein 9.46wt%.Get 20g low point of oil ingredient and be placed in separating funnel, add concentration be 30wt% sodium carbonate solution 40g mix and with the speed of 180r/min stir 30min, the envrionment temperature stirred is 30 DEG C, stratification 35min, is then separated and obtains the first aqueous phase solution and oil-phase solution.Improve one's methods with GB/T24207-2009 and measure the phenol content of oil-phase solution, obtain phenol content in oil-phase solution and drop to 1.36wt%.Below carbonic acid gas adjust ph to 6.0 is passed in first aqueous phase solution, methylene dichloride is added after being cooled to 15 DEG C, and stir 20min with the speed of 180r/min, the volume ratio of methylene dichloride and the second aqueous phase solution is 1:2, be separated the organic phase solution obtaining enrichment phenolic compound after stratification 30min, concrete operating parameters is in table 1.The rate of recovery adopting vapor-phase chromatography measurement to obtain phenol is 92.53%., in aqueous phase, the rear sodium carbonate rate of recovery is dried in solute dehydration is 89.65%, and concrete test result is in table 2.
Embodiment 17
To contain a certain amount of gelatin liquefaction low point of oil 78 ~ 270 DEG C of cuts for raw material, total phenol content is wherein 9.45wt%.Get 20g low point of oil 78 ~ 270 DEG C of cuts and be placed in separating funnel, add concentration be 30wt% sodium carbonate solution 40g mix and with the speed of 180r/min stir 30min, the envrionment temperature stirred is 30 DEG C, stratification 30min, is then separated and obtains the first aqueous phase solution and oil-phase solution.Improve one's methods with GB/T24207-2009 and measure the phenol content of oil-phase solution, obtain phenol content in oil-phase solution and drop to 1.15wt%.Below carbonic acid gas adjust ph to 6.0 is passed in second aqueous phase solution, methylene dichloride is added after being cooled to 15 DEG C, and stir 20min with the speed of 180r/min, the volume ratio of methylene dichloride and the first aqueous phase solution is 1:1, be separated the organic phase solution obtaining enrichment phenolic compound after stratification 30min, concrete operating parameters is in table 1.The rate of recovery adopting vapor-phase chromatography measurement to obtain phenol is 94.64%, and in aqueous phase, the rear sodium carbonate rate of recovery is dried in solute dehydration is 86.99%, and concrete test result is in table 2.
Embodiment 18
To contain a certain amount of gelatin liquefaction flash oil 170 ~ 310 DEG C for raw material, total phenol content is wherein 7.30wt%.Get 20g raw material and be placed in separating funnel, add the sodium sulfite solution 40g that concentration is 30wt%, operating process is identical with embodiment 17, and concrete operating parameters is in table 1, and test result is in table 2.
Embodiment 19
To contain a certain amount of gelatin liquefaction flash oil 170 ~ 310 DEG C for raw material, total phenol content is wherein 7.30wt%.Get 20g raw material and be placed in separating funnel, add the sodium sulfite solution 40g that concentration is 30wt%, operating process is identical with embodiment 17, and concrete operating parameters is in table 1, and test result is in table 2.
Comparative example
To contain a certain amount of gelatin liquefaction flash oil 170 ~ 310 DEG C for raw material, total phenol content is wherein 7.30wt%.Get 25g raw material and be placed in separating funnel, add the sodium hydroxide solution 25g that concentration is 20wt%, mix and stir 30min, stratification 30min, be then separated and obtain the first aqueous phase solution and oil-phase solution.Improve one's methods with GB/T24207-2009 and measure the phenol content of oil-phase solution, obtain phenol content in oil-phase solution and drop to 0.39%.10% sulphuric acid soln is added in first aqueous phase solution, below adjust ph to 6.0, to 20 DEG C after cooling, add methylene dichloride, mix and blend 30min, the volume ratio of methylene dichloride and the first aqueous phase solution is 1:1, is separated the organic phase solution obtaining enrichment phenolic compound after stratification 30min, and the rate of recovery adopting vapor-phase chromatography method to measure phenol is 95.07.
Table 1
Table 2
Known from the test result of table 2: the extracting method of the application effectively can extract the phenolic compound liquefied coal coil, and when the weight ratio of alkaline salt solution and liquefied coal coil is between 1:2 ~ 6:2, the mass concentration of alkaline salt solution is between 5% ~ 30%, stirring velocity in step S1 is between 60 ~ 180r/min, churning time is between 5 ~ 60min, and the envrionment temperature stirred is between 20 DEG C ~ 80 DEG C, the time left standstill of step S2 is between 5 ~ 60min, the volume ratio of organic solution and the second aqueous phase solution is between 1:3 ~ 1:1, organic solvent is methylene dichloride and/or octanol, the stirring velocity of step S42 is between 60 ~ 180r/min, churning time is between 5 ~ 20min, time of repose in step S43 is between 5 ~ 60min, in step S41, the second aqueous phase solution is cooled between 15 ~ 20 DEG C, the rate of recovery of phenol is higher, between 94.82% ~ 95.18%, the application only need adopt the alkaline salt solution of strong base weak acid just the phenolic compound in liquefied coal coil can be extracted, and it is suitable with the phenol rate of recovery in comparative example, even also high, meanwhile, the rate of recovery of the sodium carbonate of the method, between 81.08% ~ 86.79%, avoids the problem of the waste liquid difficulty recovery generated when adopting strong acid or highly basic to extract, and then avoids the pollution to environment.As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
In the extracting method of the application, first liquefied coal coil and alkaline salt solution are mixed to form the first mixing solutions, phenolic compound has slightly acidic, can react with the alkaline salt solution of strong base weak acid, phenolic compound is transferred in aqueous phase from liquefied coal coil, and the hydrocarbons in liquefied coal coil can not react with alkaline salt solution, so adopt the phenolic compound in strong base-weak acid salt solution separating liquefied coal coil to have good selectivity and higher resolution; Then, be separated the aqueous phase of above-mentioned first mixing solutions, obtain the first aqueous phase solution, the first aqueous phase solution comprises basic salt and phenates, and does not comprise the hydrocarbons in liquefied coal coil, the phenolic compound in liquefied coal coil and hydrocarbons is separated like this; Finally the pH value of above-mentioned first aqueous phase solution is adjusted to and is less than 6.0, make solution be acid, neutralize the second aqueous phase solution that the basic salt of the first aqueous phase solution and phenates obtain containing phenolic compound again.
Above-mentioned extracting method, only the alkaline salt solution of strong base weak acid need be adopted just the phenolic compound in liquefied coal coil can be extracted, overcome in prior art and adopt phenolic compound in highly basic or strong acid extraction liquefied coal coil to the heavy corrosion of extraction equipment; Meanwhile, the waste of the generation of present method is easier to reclaim, and it also avoid the difficult problem reclaimed of waste liquid generated when adopting strong acid or highly basic to extract, and then avoids the pollution to environment.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. the extracting method of phenolic compound in liquefied coal coil, it is characterized in that, described extracting method comprises:
Step S1, is mixed to form the first mixing solutions by liquefied coal coil and alkaline salt solution;
Step S2, is separated the aqueous phase of described first mixing solutions, obtains the first aqueous phase solution; And
Step S3, is adjusted to the pH value of described first aqueous phase solution and is less than 6.0, obtain the second aqueous phase solution containing phenolic compound.
2. extracting method according to claim 1, is characterized in that, the weight ratio of described alkaline salt solution and liquefied coal coil is 1:2 ~ 6:2.
3. extracting method according to claim 1, is characterized in that, the mass concentration of described alkaline salt solution is 5% ~ 30%, and preferred described alkaline salt solution is sodium carbonate, S-WAT or salt of wormwood.
4. extracting method according to claim 1, is characterized in that, described step S1 adopts the stirring velocity of 60r/min ~ 180r/min to stir 5 ~ 60min and obtains described first mixing solutions, and the envrionment temperature of preferred described stirring is 20 DEG C ~ 80 DEG C.
5. extracting method according to claim 1, is characterized in that, described step S2 comprises:
Leave standstill aqueous phase and oil phase that described mixing solutions obtains layering, isolate described aqueous phase and obtain described first aqueous phase solution, the described standing time is 5 ~ 60min.
6. extracting method according to claim 1, is characterized in that, described step S3 adopt in described first aqueous phase solution, pass into carbonic acid gas method by the pH regulator of described first aqueous phase solution to being less than 6.0.
7. extracting method according to claim 1, is characterized in that, described extracting method also comprises after described step S3:
Step S4, mixes described second aqueous phase solution with organic solvent, obtains the organic phase solution containing described phenolic compound.
8. extracting method according to claim 7, is characterized in that, described step S4 comprises:
Step S41, is cooled to 15 ~ 20 DEG C by described second aqueous phase solution;
Step S42, mixes described second aqueous phase solution with described organic solvent, obtains the second mixing solutions; And
Step S43, leaves standstill described second mixing solutions, and be separated and obtain organic phase solution and the 3rd aqueous phase solution, the described standing time is 5 ~ 60min.
9. extracting method according to claim 7, is characterized in that, the volume ratio of described organic solution and described second aqueous phase solution is between 1:3 ~ 1:1.
10. the extracting method according to any one of claim 7 to 9, is characterized in that, described organic solvent is methylene dichloride and/or octanol.
11. extracting method according to claim 8, is characterized in that, described step S42 adopts the stirring velocity of 60r/min ~ 180r/min to stir 5 ~ 20min and obtains described second mixing solutions.
12. extracting method according to claim 8, is characterized in that, described step S43 also comprises:
Step a, carries out drying to described 3rd aqueous phase solution, obtains enriched material; And
Step b, heats described enriched material, obtains basic salt and carbonic acid gas.
13. extracting method according to claim 12, is characterized in that, described basic salt returns described step S1 and reuses, and described carbonic acid gas returns described step S3 for regulating the pH value of described first aqueous phase solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510202567.1A CN104845662A (en) | 2015-04-24 | 2015-04-24 | A method for extracting phenolic compounds in coal liquefaction oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510202567.1A CN104845662A (en) | 2015-04-24 | 2015-04-24 | A method for extracting phenolic compounds in coal liquefaction oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104845662A true CN104845662A (en) | 2015-08-19 |
Family
ID=53845659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510202567.1A Pending CN104845662A (en) | 2015-04-24 | 2015-04-24 | A method for extracting phenolic compounds in coal liquefaction oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104845662A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034453A (en) * | 2017-11-14 | 2018-05-15 | 神华集团有限责任公司 | The method that phenolic compound is extracted from coal direct liquefaction oil |
| CN111892484A (en) * | 2020-05-27 | 2020-11-06 | 河北诚江医药科技有限公司 | Continuous decolorizing and deodorizing method for low-temperature crude phenol in coal gasification |
| CN114317973A (en) * | 2021-12-17 | 2022-04-12 | 北京工业大学 | Pyrolysis recovery method for organic components of waste light-emitting diodes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143805A (en) * | 2006-09-15 | 2008-03-19 | 中国石油化工股份有限公司 | Method for separating phenols compounds from phenol-containing raw material oil |
| CN102719267A (en) * | 2012-06-28 | 2012-10-10 | 神华集团有限责任公司 | Separation method for phenolic compound in coal liquefied oil |
| CN102731262A (en) * | 2012-06-18 | 2012-10-17 | 袁振 | Method for recovering phenolic compounds from coal-derived oil products |
| CN103965950A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
-
2015
- 2015-04-24 CN CN201510202567.1A patent/CN104845662A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143805A (en) * | 2006-09-15 | 2008-03-19 | 中国石油化工股份有限公司 | Method for separating phenols compounds from phenol-containing raw material oil |
| CN102731262A (en) * | 2012-06-18 | 2012-10-17 | 袁振 | Method for recovering phenolic compounds from coal-derived oil products |
| CN102719267A (en) * | 2012-06-28 | 2012-10-10 | 神华集团有限责任公司 | Separation method for phenolic compound in coal liquefied oil |
| CN103965950A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
Non-Patent Citations (1)
| Title |
|---|
| 包文杰 等: "碱盐法从煤液化油中分离提取酣类化合物的初步研究", 《化学世界 增刊》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034453A (en) * | 2017-11-14 | 2018-05-15 | 神华集团有限责任公司 | The method that phenolic compound is extracted from coal direct liquefaction oil |
| CN111892484A (en) * | 2020-05-27 | 2020-11-06 | 河北诚江医药科技有限公司 | Continuous decolorizing and deodorizing method for low-temperature crude phenol in coal gasification |
| CN111892484B (en) * | 2020-05-27 | 2023-06-20 | 河北正华科技有限公司 | Continuous decoloring and deodorizing method for low-temperature crude phenol in coal gasification |
| CN114317973A (en) * | 2021-12-17 | 2022-04-12 | 北京工业大学 | Pyrolysis recovery method for organic components of waste light-emitting diodes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102219649B (en) | Method of extracting phenolic compound from coal liquefied oil or coal tar | |
| CN103965950B (en) | Method for separating phenols in coal liquefaction oil | |
| CN102127008B (en) | Method for recycling pyridine from chemical production wastewater | |
| CN107118756B (en) | A kind of efficient thick-oil thinner and preparation method thereof | |
| CN106432368A (en) | Method of efficiently extracting fulvic acid from papermaking black liquid | |
| CN105502551A (en) | Technology for recycling lithium from industrial wastewater | |
| CN104845662A (en) | A method for extracting phenolic compounds in coal liquefaction oil | |
| CN102936051A (en) | Process for treating dinaphthol wastewater by using complexation extraction method | |
| CN104946303B (en) | A kind of method of phenol mixture in Selective Separation oil | |
| CN104649898B (en) | A kind of solvent method continuous carbonization produces beta naphthal, the method and device of coproduction 2,3 acid | |
| CN100420508C (en) | Microemulsion and its preparation process and use in treating industrial phenolic waste water | |
| CN109810159A (en) | A kind of method that allocholic acid yield can be improved from duck bile | |
| CN100999480A (en) | Process for recovering dimethyl formyl amine from waste water using ion liquid extracting process | |
| CN105129894B (en) | A kind of T-acid mother liquor Efficient extraction method | |
| CN103396827B (en) | The separation method of liquefied coal coil neutral and alkali nitrogen compound | |
| CN102115224B (en) | Method for pretreating production waste water of fenoxaprop pesticide | |
| CN102936052B (en) | Method for recycling carboxymethylcellulose production wastewater | |
| CN105084634A (en) | Pretreatment method of rubber ingredient production wastewater | |
| CN113462466B (en) | Method for extracting and separating grease from seaweed | |
| CN102241580A (en) | Method for recovering organic carboxylic acids from corn chemical alcohol reaction kettle residues by utilizing complex extraction | |
| CN108046366A (en) | A kind of High-Efficiency Phenol-Degradation extractant and its method for extracting and dephenolizing | |
| CN107746402A (en) | Ultrasonic assistant deodorization distillate extracts tocopherol and metal zinc salt synchronization recovery method | |
| CN106242950B (en) | A method of preparing pyrogallic acid | |
| CN105967211B (en) | Method for preparing potassium sulfate from brine | |
| CN106635144A (en) | Method for enriching and separating phenolic compounds in shale oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150819 |