CN104327876A - Method for extracting oxides from oil shale through step-by-step oxidization - Google Patents
Method for extracting oxides from oil shale through step-by-step oxidization Download PDFInfo
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Abstract
The invention discloses a method for extracting oxides from oil shale through step-by-step oxidization, belonging to the technical field of oil shale processing, and in particular relates to a method for extracting oxides from oil shale through step-by-step oxidization, in order to solve a problem of low oil shale utilization rate in the prior art. The method comprises the steps of de-ashing HCl, oxidizing oil shale which is less than 0.90mm in granularity through nitric acid, hydrogen peroxide, acidified sodium hypochlorite and ozone sequentially step by step, conducting solvent extraction to shale oil oxidized in each step, and using extract in the prior step as an oxidized object in next step. The method disclosed by the invention is used for extracting oxides from the oil shale.
Description
Technical field
The invention belongs to oil shale processing technique field, be specifically related to the method for oxide compound in a kind of resinous shale of oxidative extraction step by step.
Background technology
Resinous shale is a kind of high-ash solid combustible organic sedimentary rock, and low-temperature pyrolysis can obtain shale oil, oil length >3.5%, the general >4.18MJ/Kg of thermal value.Resinous shale is made up of inorganic mineral and organic matter, and wherein the content of inorganic mineral is higher than the content of organic matter.The content of the organic matter of China's resinous shale accounts for 10% ~ 25% of resinous shale quality usually, is generally no more than 45%, and organic matter is petrologen (oil is female) mainly, also has a small amount of solvable pitch in addition.Resinous shale is heated to about 500 DEG C, and its petrologen pyrolysis generates shale oil.
Resinous shale is a kind of unconventional resource.At present, the explored reserves in the world (amounting to into shale oil) are about 4750 × 10
8t, 5.4 times that are equivalent to that workable reserve verified by world's crude oil.The oil shale deposits of China occupies the 4th, the world, has huge reserves and potential value.
At present, the utilization ways of resinous shale mainly contains three kinds: directly burn as fuel, combustion power generation, destructive distillation produce shale oil.But three kinds of utilization ways are while make use of oil shale resources, also all there is certain drawback, wherein direct burning and the combustion power generation problem that all burning that is that exist is insufficient, capacity usage ratio is low because the thermal value of resinous shale is not high, the problem that shale oil process exists macromole carbon compound coking in oily mother is produced in destructive distillation, and organic utilization ratio is reduced greatly.Other Application way, as the solvent extraction of resinous shale, are only limitted to laboratory and lab scale stage at present.
Also scholar is had to carry out peroxidation research to resinous shale, the method for oxidation adopted is potassium permanganate oxidation, nitric acid oxidation, electrochemical oxidation process produce organic acid, these method for oxidation are stair oxidation, product is organic acid, and oxidation is not thorough, major part organic matter in resinous shale is still present in extract remainder with the form of fixed carbon, causes the waste of oil shale resources.
If a kind of new resinous shale processing approach can be inquired into out, produce the product that added value is higher, which not only improves the utility value of resinous shale, and likely replace a part of natural oil, the contradiction relaxing petroleum resources anxiety is had great importance.
Summary of the invention
The present invention will solve the low problem of existing resinous shale utilization ratio, and provides the method for oxide compound in a kind of resinous shale of oxidative extraction step by step.
In a kind of oxidative extraction step by step of the present invention resinous shale, the method for oxide compound is carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale step one obtained loads in acid-resistant reactor, the nitric acid that volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 100 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 40 DEG C ~ 90 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; The quality of the resinous shale that described step one obtains and volume fraction are the volume ratio of the nitric acid of 30% is 1g:(5 ~ 10) mL;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the superoxol that massfraction is 30% is added in second reactor, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 70 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hydrogen peroxide oxidation liquid A2 and hydrogen peroxide oxidation resinous shale B2 respectively, hydrogen peroxide oxidation resinous shale B2 is put into extractor, under the condition of 40 DEG C ~ 56 DEG C of normal pressures, with acetone extract 4h ~ 8h, through filtering after extraction, washing is separated, obtain acetone extract remainder C2 and acetone extract liquid D2, the quality of the sherwood oil extract remainder C1 that described step 2 obtains and massfraction are the volume ratio of the superoxol of 30% is 1g:(5 ~ 10) mL,
Four, the third stage is oxidized: acetone extract remainder C2 step 3 obtained loads in three reactor, the massfraction adding pH=1 in three reactor is the chlorine bleach liquor of 8%, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 100 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hypochlorite oxidation liquid A3 and hypochlorite oxidation resinous shale B3 respectively, hypochlorite oxidation resinous shale B3 is put into extractor, under the condition of 40 DEG C ~ 64 DEG C of normal pressures, with methanol extraction 4h ~ 8h, through filtering after extraction, washing is separated, obtain methyl alcohol extract remainder C3 and methanol extraction liquid D3, the quality of acetone extract remainder C2 that described step 3 obtains and the massfraction of pH=1 are the volume ratio of the chlorine bleach liquor of 8% is 1g:(5 ~ 10) mL,
Five, fourth stage oxidation: methyl alcohol extract remainder C3 step 4 obtained puts into fluidized-bed reaction producer, ozone oxidation 1.5h ~ 3h is passed in fluidized-bed reaction producer, obtain ozone oxidation resinous shale B4, ozone oxidation resinous shale B4 is put into extractor, under the condition of 40 DEG C ~ 64 DEG C of normal pressures, with methanol extraction 4h ~ 8h, be separated through filtering, washing after extraction, obtain methyl alcohol extract remainder C4 and methanol extraction liquid D4; The described flow velocity passing into ozone is 0.1h
-1~ 1.0h
-1.
Principle: select oxygenant to be oxidized mother oily in resinous shale in the present invention, the size of the electrode potential numerical value of oxygenant and oxide reflects the power that electric centering oxidized form material obtains electronics and reducing substances betatopic ability.In the present invention, oxygenant selects nitric acid, hydrogen peroxide, clorox, ozone to be as the reason of oxygenant successively step by step:
1, nitric acid, hydrogen peroxide, clorox and ozone are in oxidising process, other impurity can not be introduced in resinous shale oxidation residues, prevent resinous shale hole blocked, be conducive to the diffusion of the extraction process extraction agent of oxidation residues at different levels, increase the duration of contact of extraction agent and oxidized resinous shale;
2, nitric acid, hydrogen peroxide, clorox and ozone are all micromolecular compounds, and molecular radical is little, is easy to react with oil mother.
The select progressively principle being oxidized oxygenant is step by step: the order that oxygenant grows from weak to strong according to redox-potential be oxidized with reactant successively, obtain the oxidation products of different oxidation depth.
The Standard Electrode Potentials of four kinds of oxygenants:
Nitric acid:
Clorox:
Hydrogen peroxide:
Ozone:
According to Nernst equation:
Calculate the Conditional electrode potential of nitric acid under the process conditions, volume fraction is the concentration of the nitric acid of 30% is 5.41mol/L.
The electrode potential of calculated hydrogen oxide under the process conditions, superoxol PH=6
Because there is reaction in hydrogen peroxide
Calculate the electrode potential of clorox under the process conditions.Chlorine bleach liquor PH=1, the condition of Nernst equation is PH=1, and therefore, the Standard Electrode Potentials of clorox is exactly Conditional electrode potential.
Calculate the electrode potential of ozone under the process conditions.Under standard pressure, the Standard Electrode Potentials of ozone is 2.03.Experiment carries out under standard pressure, and therefore, the Standard Electrode Potentials of ozone is exactly experiment condition electrode potential.
According to relatively can find out Conditional electrode potential electropotential, the Conditional electrode potential of nitric acid condition electropotential 0.933, hydrogen peroxide is 1.094, the Conditional electrode potential of clorox is 1.482, the Conditional electrode potential of ozone is 2.03.The present invention step by step oxidation sequence is the arrangement that grows from weak to strong according to condition electropotential, so obtaining oxidation sequence is nitric acid, hydrogen peroxide, clorox, ozone.
The invention has the beneficial effects as follows:
1, the present invention adopts to be oxidized step by step and extracts resinous shale, the total oxidative extraction rate of resinous shale being 54.14% for ash content all (accounts for the weight ratio of resinous shale) more than 36%, resinous shale ash content after oxidation/extraction, higher than 85.00%, ensure that high extraction organic in resinous shale.Oxidative extraction product containing various ingredients such as organic acid, hydro carbons, alcohols, adds the added value of resinous shale extract by analysis.
2, the present invention adopts nitric acid, hydrogen peroxide, clorox and ozone to be oxidized step by step, other impurity can not be introduced in resinous shale oxidation residues, prevent resinous shale hole blocked, be conducive to the diffusion of the extraction process extraction agent of oxidation residues at different levels, increase the duration of contact of extraction agent and oxidized resinous shale; Nitric acid, hydrogen peroxide, clorox and ozone are all micromolecular compounds simultaneously, and molecular radical is little, is easy to react with oil mother.
Embodiment
Embodiment one: in a kind of resinous shale of oxidative extraction step by step described in present embodiment, the method for oxide compound is carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale step one obtained loads in acid-resistant reactor, the nitric acid that volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 100 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 40 DEG C ~ 90 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; The quality of the resinous shale that described step one obtains and volume fraction are the volume ratio of the nitric acid of 30% is 1g:(5 ~ 10) mL;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the superoxol that massfraction is 30% is added in second reactor, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 70 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hydrogen peroxide oxidation liquid A2 and hydrogen peroxide oxidation resinous shale B2 respectively, hydrogen peroxide oxidation resinous shale B2 is put into extractor, under the condition of 40 DEG C ~ 56 DEG C of normal pressures, with acetone extract 4h ~ 8h, through filtering after extraction, washing is separated, obtain acetone extract remainder C2 and acetone extract liquid D2, the quality of the sherwood oil extract remainder C1 that described step 2 obtains and massfraction are the volume ratio of the superoxol of 30% is 1g:(5 ~ 10) mL,
Four, the third stage is oxidized: acetone extract remainder C2 step 3 obtained loads in three reactor, the massfraction adding pH=1 in three reactor is the chlorine bleach liquor of 8%, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 100 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hypochlorite oxidation liquid A3 and hypochlorite oxidation resinous shale B3 respectively, hypochlorite oxidation resinous shale B3 is put into extractor, under the condition of 40 DEG C ~ 64 DEG C of normal pressures, with methanol extraction 4h ~ 8h, through filtering after extraction, washing is separated, obtain methyl alcohol extract remainder C3 and methanol extraction liquid D3, the quality of acetone extract remainder C2 that described step 3 obtains and the massfraction of pH=1 are the volume ratio of the chlorine bleach liquor of 8% is 1g:(5 ~ 10) mL,
Five, fourth stage oxidation: methyl alcohol extract remainder C3 step 4 obtained puts into fluidized-bed reaction producer, ozone oxidation 1.5h ~ 3h is passed in fluidized-bed reaction producer, obtain ozone oxidation resinous shale B4, ozone oxidation resinous shale B4 is put into extractor, under the condition of 40 DEG C ~ 64 DEG C of normal pressures, with methanol extraction 4h ~ 8h, be separated through filtering, washing after extraction, obtain methyl alcohol extract remainder C4 and methanol extraction liquid D4; The described flow velocity passing into ozone is 0.1h
-1~ 1.0h
-1.
Present embodiment adopts to be oxidized step by step and extracts resinous shale, the total oxidative extraction rate of resinous shale being 54.14% for ash content all (accounts for the weight ratio of resinous shale) more than 36%, resinous shale ash content after oxidation/extraction, higher than 85.00%, ensure that high extraction organic in resinous shale.Oxidative extraction product containing various ingredients such as organic acid, hydro carbons, alcohols, adds the added value of resinous shale extract by analysis.
Present embodiment adopts nitric acid, hydrogen peroxide, clorox and ozone to be oxidized step by step, other impurity can not be introduced in resinous shale oxidation residues, prevent resinous shale hole blocked, be conducive to the diffusion of the extraction process extraction agent of oxidation residues at different levels, increase the duration of contact of extraction agent and oxidized resinous shale; Nitric acid, hydrogen peroxide, clorox and ozone are all micromolecular compounds simultaneously, and molecular radical is little, is easy to react with oil mother.
Embodiment two: present embodiment and embodiment one unlike: under the condition of 80 DEG C of normal pressures, be oxidized 1.5h ~ 3h in step 2.Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: in step 2 under the condition of 60 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h.Other are identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one to three unlike: under the condition of 60 DEG C of normal pressures, be oxidized 1.5h ~ 3h in step 3.Other are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: in step 3 under the condition of 50 DEG C of normal pressures, with acetone extract 4h ~ 8h.Other are identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: under the condition of 80 DEG C of normal pressures, be oxidized 1.5h ~ 3h in step 4.Other are identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in step 4 under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h.Other are identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: in step 5 under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h.Other are identical with one of embodiment one to seven.
Beneficial effect of the present invention is verified by following examples:
Embodiment one: in a kind of resinous shale of oxidative extraction step by step, the method for oxide compound is carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale 500g step one obtained loads in acid-resistant reactor, the nitric acid that 2.5L volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 60 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; Through calculating of weighing, first step oxidation/leaching process, the oxidative extraction rate of resinous shale is 9.46%;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the superoxol that 2.5L massfraction is 30% is added in second reactor, 1.5h ~ 3h is oxidized under the condition of 60 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hydrogen peroxide oxidation solution A2 and hydrogen peroxide oxidation resinous shale B2 respectively, hydrogen peroxide oxidation resinous shale B2 is put into extractor, under the condition of 50 DEG C of normal pressures, with acetone extract 4h ~ 8h, through filtering after extraction, washing is separated, obtain acetone extract remainder C2 and acetone extract liquid D2, through calculating of weighing, second stage oxidation/leaching process, the oxidative extraction rate of resinous shale is 22.17%,
Four, the third stage is oxidized: acetone extract remainder C2 step 3 obtained loads in three reactor, the massfraction adding 2.5LpH=1 in three reactor is the chlorine bleach liquor of 8%, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hypochlorite oxidation liquid A3 and hypochlorite oxidation resinous shale B3 respectively, hypochlorite oxidation resinous shale B3 is put into extractor, under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h, through filtering after extraction, washing is separated, obtain methyl alcohol extract remainder C3 and methanol extraction liquid D3, through calculating of weighing, third stage oxidation/leaching process, the oxidative extraction rate of resinous shale is 17.36%,
Five, fourth stage oxidation: methyl alcohol extract remainder C3 step 4 obtained puts into fluidized-bed reaction producer, ozone oxidation 1.5h ~ 3h is passed in fluidized-bed reaction producer, obtain ozone oxidation resinous shale B4, ozone oxidation resinous shale B4 is put into extractor, under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h, be separated through filtering, washing after extraction, obtain methyl alcohol extract remainder C4 and methanol extraction liquid D4; The described flow velocity passing into ozone is 0.1h
-1~ 1.0h
-1; Through calculating of weighing, fourth stage oxidation/leaching process, the oxidative extraction rate of resinous shale is 4.92%.
Through oxidation step by step and the extraction of level Four, calculate total extraction yield and ash content, wherein total extraction yield calculation formula is as follows:
Former state: the quality that resinous shale is weighed, g
Final extract: the extract remainder quality obtained after fourth stage ozone oxidation and methanol extraction, g
After level Four oxidation, the total extraction yield of resinous shale is 45.44%, and the ash content of final extract remainder is 96.73%.
Embodiment two: in a kind of resinous shale of oxidative extraction step by step, the method for oxide compound is carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale 500g step one obtained loads in acid-resistant reactor, the nitric acid that 2.5L volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 60 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; Through calculating of weighing, first step oxidation/leaching process, the oxidative extraction rate of resinous shale is 9.46%;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the superoxol that 2.5L massfraction is 30% is added in second reactor, 1.5h ~ 3h is oxidized under the condition of 60 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hydrogen peroxide oxidation solution A2 and hydrogen peroxide oxidation resinous shale B2 respectively, hydrogen peroxide oxidation resinous shale B2 is put into extractor, under the condition of 50 DEG C of normal pressures, with acetone extract 4h ~ 8h, through filtering after extraction, washing is separated, obtain acetone extract remainder C2 and acetone extract liquid D2, through calculating of weighing, second stage oxidation/leaching process, the oxidative extraction rate of resinous shale is 22.17%,
Four, the third stage is oxidized: acetone extract remainder C2 step 3 obtained loads in three reactor, the massfraction adding 2.5LpH=1 in three reactor is the chlorine bleach liquor of 8%, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hypochlorite oxidation liquid A3 and hypochlorite oxidation resinous shale B3 respectively, hypochlorite oxidation resinous shale B3 is put into extractor, under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h, through filtering after extraction, washing is separated, obtain methyl alcohol extract remainder C3 and methanol extraction liquid D3, through calculating of weighing, third stage oxidation/leaching process, the oxidative extraction rate of resinous shale is 17.36%.
The present embodiment is through three grades of oxidation and extractions step by step, and the total extraction yield of resinous shale is 40.52%, and after tertiary oxidation, the ash content of resinous shale is 91.68%.
Embodiment three: in a kind of resinous shale of oxidative extraction step by step, the method for oxide compound is carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale 500g step one obtained loads in acid-resistant reactor, the nitric acid that 2.5L volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 60 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; Through calculating of weighing, first step oxidation/leaching process, the oxidative extraction rate of resinous shale is 9.46%;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the superoxol that 2.5L massfraction is 30% is added in second reactor, 1.5h ~ 3h is oxidized under the condition of 60 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hydrogen peroxide oxidation solution A2 and hydrogen peroxide oxidation resinous shale B2 respectively, hydrogen peroxide oxidation resinous shale B2 is put into extractor, under the condition of 50 DEG C of normal pressures, with acetone extract 4h ~ 8h, through filtering after extraction, washing is separated, obtain acetone extract remainder C2 and acetone extract liquid D2, through calculating of weighing, second stage oxidation/leaching process, the oxidative extraction rate of resinous shale is 22.17%,
Four, third stage oxidation: acetone extract remainder C2 step 3 obtained puts into fluidized-bed reaction producer, ozone oxidation 1.5h ~ 3h is passed in fluidized-bed reaction producer, obtain ozone oxidation resinous shale B4, ozone oxidation resinous shale B4 is put into extractor, under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h, be separated through filtering, washing after extraction, obtain methyl alcohol extract remainder C4 and methanol extraction liquid D4; The described flow velocity passing into ozone is 0.1h
-1~ 1.0h
-1.
The present embodiment is through three grades of oxidation and extractions step by step, and the total extraction yield of resinous shale is 36.74%, and after tertiary oxidation, the ash content of resinous shale is 85.38%.
Embodiment four: in a kind of resinous shale of oxidative extraction step by step, the method for oxide compound is carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale 500g step one obtained loads in acid-resistant reactor, the nitric acid that 2.5L volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 60 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; Through calculating of weighing, first step oxidation/leaching process, the oxidative extraction rate of resinous shale is 9.46%;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the massfraction adding 2.5LpH=1 in second reactor is the chlorine bleach liquor of 8%, 1.5h ~ 3h is oxidized under the condition of 80 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hypochlorite oxidation liquid A3 and hypochlorite oxidation resinous shale B3 respectively, hypochlorite oxidation resinous shale B3 is put into extractor, under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h, through filtering after extraction, washing is separated, obtain methyl alcohol extract remainder C3 and methanol extraction liquid D3,
Four, third stage oxidation: methyl alcohol extract remainder C3 step 3 obtained puts into fluidized-bed reaction producer, ozone oxidation 1.5h ~ 3h is passed in fluidized-bed reaction producer, obtain ozone oxidation resinous shale B4, ozone oxidation resinous shale B4 is put into extractor, under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h, be separated through filtering, washing after extraction, obtain methyl alcohol extract remainder C4 and methanol extraction liquid D4; The described flow velocity passing into ozone is 0.1h
-1~ 1.0h
-1.
Through three grades of oxidation and extractions step by step, the total extraction yield of resinous shale is 38.26%, and after tertiary oxidation, the ash content of resinous shale is 88.45%.
Embodiment five: the present embodiment and embodiment one difference be stair oxidation, secondary oxidation, tertiary oxidation and level Four be oxidized in extraction agent used be acetone, the washings of extraction process filter cake is acetone, and in extraction process, extraction temperature is the boiling temperature 56 DEG C of acetone.Other operational conditions are identical with embodiment one.Through oxidation step by step and the extraction of level Four, the total extraction yield of resinous shale is 45.07%, and after level Four oxidation, the ash content of resinous shale is 96.19%.
Embodiment six: the present embodiment and embodiment one difference be stair oxidation, secondary oxidation, tertiary oxidation and level Four be oxidized in extraction agent used be sherwood oil, the washings of extraction process filter cake is sherwood oil, and in extraction process, extraction temperature is the boiling temperature 60 ~ 90 DEG C of sherwood oil.Other operational conditions are identical with embodiment one.Be 42.47% through the oxidation step by step of level Four with extracting resinous shale total extraction yield, after level Four oxidation, the ash content of resinous shale is 93.46%.
Embodiment seven: the present embodiment and embodiment one difference be stair oxidation, secondary oxidation, tertiary oxidation and level Four be oxidized in extraction agent used be methyl alcohol, the washings of extraction process filter cake is methyl alcohol, and in extraction process, extraction temperature is the boiling temperature 65 DEG C of methyl alcohol.Other operational conditions are identical with embodiment one.Through oxidation step by step and the extraction of level Four, the total extraction yield of resinous shale is 40.57%, and after level Four oxidation, the ash content of resinous shale is 91.61%.
Claims (8)
1. the method for oxide compound in oxidative extraction resinous shale step by step, is characterized in that the method for oxide compound in oxidative extraction resinous shale is step by step carried out according to the following steps:
One, resinous shale primary sample is crushed to granularity and is less than 0.90mm, with rare HCl deliming, obtain resinous shale;
Two, first step oxidation: resinous shale step one obtained loads in acid-resistant reactor, the nitric acid that volume fraction is 30% is added in acid-resistant reactor, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 100 DEG C of normal pressures, then adopt acidproof strainer to carry out filtering, washing separation, obtain nitric acid oxidation liquid A1 and nitric acid oxidation resinous shale B1; Nitric acid oxidation resinous shale B1 is put into extractor, under the condition of 40 DEG C ~ 90 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h, is separated through filtering, washing after extraction, obtains sherwood oil extract remainder C1 and petroleum ether extraction liquid D1; The quality of the resinous shale that described step one obtains and volume fraction are the volume ratio of the nitric acid of 30% is 1g:(5 ~ 10) mL;
Three, the second stage is oxidized: sherwood oil extract remainder C1 step 2 obtained loads in second reactor, the superoxol that massfraction is 30% is added in second reactor, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 70 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hydrogen peroxide oxidation liquid A2 and hydrogen peroxide oxidation resinous shale B2 respectively, hydrogen peroxide oxidation resinous shale B2 is put into extractor, under the condition of 40 DEG C ~ 56 DEG C of normal pressures, with acetone extract 4h ~ 8h, through filtering after extraction, washing is separated, obtain acetone extract remainder C2 and acetone extract liquid D2, the quality of the sherwood oil extract remainder C1 that described step 2 obtains and massfraction are the volume ratio of the superoxol of 30% is 1g:(5 ~ 10) mL,
Four, the third stage is oxidized: acetone extract remainder C2 step 3 obtained loads in three reactor, the massfraction adding pH=1 in three reactor is the chlorine bleach liquor of 8%, 1.5h ~ 3h is oxidized under the condition of 40 DEG C ~ 100 DEG C of normal pressures, then strainer is adopted to filter, washing is separated, obtain hypochlorite oxidation liquid A3 and hypochlorite oxidation resinous shale B3 respectively, hypochlorite oxidation resinous shale B3 is put into extractor, under the condition of 40 DEG C ~ 64 DEG C of normal pressures, with methanol extraction 4h ~ 8h, through filtering after extraction, washing is separated, obtain methyl alcohol extract remainder C3 and methanol extraction liquid D3, the quality of acetone extract remainder C2 that described step 3 obtains and the massfraction of pH=1 are the volume ratio of the chlorine bleach liquor of 8% is 1g:(5 ~ 10) mL,
Five, fourth stage oxidation: methyl alcohol extract remainder C3 step 4 obtained puts into fluidized-bed reaction producer, ozone oxidation 1.5h ~ 3h is passed in fluidized-bed reaction producer, obtain ozone oxidation resinous shale B4, ozone oxidation resinous shale B4 is put into extractor, under the condition of 40 DEG C ~ 64 DEG C of normal pressures, with methanol extraction 4h ~ 8h, be separated through filtering, washing after extraction, obtain methyl alcohol extract remainder C4 and methanol extraction liquid D4; The described flow velocity passing into ozone is 0.1h
-1~ 1.0h
-1.
2. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that under the condition of 80 DEG C of normal pressures, being oxidized 1.5h ~ 3h in step 2.
3. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that in step 2 under the condition of 60 DEG C of normal pressures, with petroleum ether extraction 4h ~ 8h.
4. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that under the condition of 60 DEG C of normal pressures, being oxidized 1.5h ~ 3h in step 3.
5. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that in step 3 under the condition of 50 DEG C of normal pressures, with acetone extract 4h ~ 8h.
6. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that under the condition of 80 DEG C of normal pressures, being oxidized 1.5h ~ 3h in step 4.
7. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that in step 4 under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h.
8. the method for oxide compound in a kind of resinous shale of oxidative extraction step by step according to claim 1, is characterized in that in step 5 under the condition of 55 DEG C of normal pressures, with methanol extraction 4h ~ 8h.
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| CN111234851A (en) * | 2020-02-13 | 2020-06-05 | 安徽工业大学 | Method for improving oil shale cohesiveness for coal blending and coking |
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| CN111234851B (en) * | 2020-02-13 | 2021-07-13 | 安徽工业大学 | Method for improving oil shale cohesiveness for coal blending and coking |
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