CN103464179B - Catalyst used for extracting shale oil from oil shale and application method of catalyst - Google Patents
Catalyst used for extracting shale oil from oil shale and application method of catalyst Download PDFInfo
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- CN103464179B CN103464179B CN201310441301.3A CN201310441301A CN103464179B CN 103464179 B CN103464179 B CN 103464179B CN 201310441301 A CN201310441301 A CN 201310441301A CN 103464179 B CN103464179 B CN 103464179B
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Abstract
The invention relates to a catalyst used for extracting shale oil from oil shale and an application method of the catalyst. Before destructive distillation and cracking of the oil shale, bivalent cobalt-manganese salt, water and a surfactant are mixed according to a certain proportion and prepared into a catalyst aqueous solution, the catalyst solution is sprayed on the surface of crushed oil shale, or the oil shale is immersed in the catalyst solution containing the surfactant; after the catalyst solution permeates into the oil shale, the oil shale is naturally or forcedly dried, and the shale oil is produced according to an original oil shale destructive distillation and cracking process. The catalyst is dispersed into the oil shale without changing existing destructive distillation process and device, so that the destructive distillation oil outlet flow temperature of the oil shale is decreased, the oil yield is improved, the content of unsaturated hydrocarbon is increased, the content of unsaturated hydrocarbon is reduced, the oil yield of the shale oil is improved, the energy conservation and consumption reduction are achieved, and the method is easy and convenient, and can reduce the production cost of the shale oil.
Description
Technical field
The present invention relates to a kind of catalyst, being specifically related to a kind of catalyst for extracting shale oil from oil shale and using method thereof.
Background technology
The sedimentary rock that oil shale be made up of organic, mineral matter and a small amount of moisture is low heat value solid-state sapropel quasi-fossil fuel, is planktonic organism, the corruption of residual body through up to ten thousand years of animalcule and plant and the effect generation of coalification.Wherein organic composition is baroque organic polymer body, and main component is a large amount of aliphatic compounds and a small amount of compound fragrant hydrocarbon.Cracking can generate a large amount of shale oil during organic pyrolysis in oil shale, the constituent class of shale oil and oil seemingly, the energy that oil can be replaced to become new after processing.
Along with continuous exploitation and the originally just abundant not reserves of limited fossil energy, the petroleum resources of China are day by day short, and shale oil replaces oil to be also subject to people's attention gradually.Seek the Efficient Development of oil shale and the approach of economic utilization, for alleviating energy supply and demand contradiction, promoting the development of society, be of great immediate significance.
One of important indicator of oil shale comprehensive utilization is the oil yield of oil shale, conventional method for destructive distillation is imported in gas retort by oil shale directly to heat destructive distillation, because the kerogen decomposition activation energy in oil shale is higher, kerogen decomposition produces pyrolysis product needs higher temperature, kerogen decomposes at relatively high temperatures, the easy dehydrogenation of its pyrolysis product, make the degree of unsaturation increase of char yeild increase, pyrolysis product, the oil yield of shale oil reduces.
CN1786115A discloses " a kind of Catalyst And Method taking oil-bearing rock as raw material and produce light-weight fuel oil ", the raw material weight percentage of this catalyst consists of: cobalt naphthenate 20 ~ 35%, glycol monoethyl ether 30 ~ 40%, acid activated bentonite 3 ~ 5%, tristerin 10 ~ 20%, chlorinated paraffin wax 20 ~ 37%, described chlorinated paraffin wax is technical grade chlorinated paraffin wax 70.Additionally provide the method utilizing this Catalyst Production light fuel.This catalyst effectively can reduce oil-bearing rock and produces the cost of light-weight fuel oil and improve the quality of light Fuel oil product, uses the method for this Catalyst Production light-weight fuel oil to break traditions under the condition of high pressure, hydrogenation technique, need distill the method for light-weight fuel oil from oil-bearing rock.
CN101962559A discloses " a kind of oil shale class ore produces the method for light-weight fuel oil ", be by oil shale class ore after broken, screening, under the condition adding catalyst, heat destructive distillation, produce light-weight fuel oil with this; Wherein, the catalyst total amount added is 0.8 ~ 2% of oil shale class ore weight, and adds in oil shale class ore by 30 ~ 70% wherein before heating destructive distillation, is added by remaining catalyst in oil shale class ore in retort process.
The weak point that above-mentioned technology exists is, the composition of catalyst reaches five kinds more than, and the formulation operations of catalyst is complicated, and cost is high; The component of composition catalyst is organic principle mostly, adds, affect catalytic efficiency when destructive distillation due to steam raising loss if disposable, if repeatedly add before and after oil shale retorting, catalyst uses complicated operation.
Summary of the invention:
The object of the present invention is to provide a kind of a kind of catalyst extracting shale oil for oil shale enough reducing oil shale retorting oil outlet temperature, the oil yield of raising shale oil, the content improving saturated hydrocarbons in shale oil, reduction presence of unsaturates;
Another object of the present invention is to provide a kind of using method extracting the catalyst of shale oil for oil shale.
The object of the invention is to be achieved through the following technical solutions:
Utilize divalence cobalt-manganese salt as catalyst, and the aqueous solution made containing surfactant, it is evenly sprayed at for the oil shale surface of destructive distillation or after oil shale is soaked the catalyst containing surfactant, nature or force drying oil shale, catalyst is made to evenly spread in oil shale, by raw oil shale carbonization decomposition explained hereafter shale oil.
Specifically before oil shale retorting cracking, become to contain the aqueous solution of surfactant as catalyst preparation using divalence cobalt-manganese salt, catalyst solution is sprayed at the surface of the oil shale after fragmentation, or in catalyst solution oil shale being immersed in containing surfactant, after catalyst solution infiltrates into oil shale inside, nature or force drying oil shale, by raw oil shale carbonization decomposition explained hereafter shale oil.
Extracting a catalyst for shale oil for oil shale, is be mixed by weight by divalence cobalt-manganese salt, water and surfactant, divalence cobalt-manganese salt: water: surfactant is 1:10 ~ 100:0.001 ~ 0.009.Described divalence cobalt-manganese salt is the sulfate of divalence cobalt manganese, hydrochloride or nitrate, or divalence cobalt and manganese oxide is dissolved in the salting liquid of sulfuric acid, hydrochloric acid or nitric acid gained.
Described surfactant is dodecyl sodium sulfate, neopelex, OPEO or polyethenoxy ether sodium sulfate.
Extract a using method for the catalyst of shale oil for oil shale, comprise the following steps:
A. oil shale is crushed to 75-12mm;
B. by weight, catalyst: oil shale is 1:100 ~ 1000, is evenly sprayed at the surface of the oil shale after fragmentation or is immersed in catalyst solution by oil shale, soaking 2-3 hours by catalyst;
C. natural drying or force drying;
D. shale oil is produced by cracking process.
Beneficial effect: the formula and the using method thereof that the invention provides a kind of oil shale retorting catalyst for cracking, do not change existing destructive distillation device, by catalyst is distributed in oil shale, reaches and reduce destructive distillation oil outlet temperature, raising oil yield, raising presence of unsaturates, reduction presence of unsaturates.Realize energy-saving consumption-reducing, reduce the target of shale oil production cost.Reduce oil shale retorting oil outlet temperature, improve oil yield and the saturated hydrocarbon content of shale oil; On the other hand, do not change distillation process and destructive distillation device, the easy popularization being suitable for large-scale production of method.
Detailed description of the invention:
Below in conjunction with embodiment, the present invention is further detailed, understands the present invention further, but protection scope of the present invention is not limited to these embodiments.
Extracting a catalyst for shale oil for oil shale, is be mixed by weight by divalence cobalt-manganese salt, water and surfactant, divalence cobalt-manganese salt: water: surfactant is 1:10 ~ 100:0.001 ~ 0.009.
Described divalence cobalt-manganese salt is the oxide of cobalt salt, manganese salt or its cobalt or manganese.
Described surfactant is dodecyl sodium sulfate, neopelex, OPEO or polyethenoxy ether sodium sulfate.
Extract a using method for the catalyst of shale oil for oil shale, comprise the following steps:
A. oil shale is crushed to 75-12mm;
B. by weight, catalyst: oil shale is 1:100 ~ 1000, is evenly sprayed at the surface of the oil shale after fragmentation or is immersed in catalyst solution by oil shale, soaking 2-3 hours by catalyst;
C. natural drying or force drying;
D. shale oil is produced by cracking process.
Embodiment 1:
Get eastern Jilin somewhere oil shale 50t, oil content is 13.21%, takes cobalt chloride 60kg, dodecyl sodium sulfate 0.5kg, be dissolved in 4000kg water, be mixed with the aqueous solution, with the oil shale surface of atomizers spray at granularity <75mm, stir oil shale during sprinkling and make its catalyzed agent solution complete wetting, soak 3 hours, utilize Fushun stove carbonization decomposition oil shale after natural drying, obtain shale oil 5759kg, its shale oil rate of recovery is 87.2%, and the rate of recovery improves 15.4%.
Embodiment 2:
Get Technique in Western Jilin Province somewhere oil shale 5t, oil content is 5.45%, take manganese sulfate 45kg as catalyst, polyethenoxy ether sodium sulfate 0.3kg as surfactant, be dissolved in 450kg water, be mixed with the aqueous solution, with the oil shale surface of atomizers spray at granularity <75mm, stir oil shale during sprinkling and make its catalyzed agent solution complete wetting, infiltrate 2.5 hours, Fushun stove carbonization decomposition oil shale is utilized after natural drying, obtain shale oil 235kg, its shale oil rate of recovery is 86.3%, and the rate of recovery improves 13.2%.
Embodiment 3:
Get Liaoning Middle somewhere oil shale 5t, oil content is 6.87%, take manganese sulfate 20kg and cobalt chloride 25kg as catalyst, neopelex 0.2kg is as surfactant, be dissolved in 460kg water, be mixed with the aqueous solution, with the oil shale surface of atomizers spray at granularity <70mm, stir oil shale during sprinkling and make its catalyzed agent solution complete wetting, soak 2 hours, Fushun stove carbonization decomposition oil shale is utilized after natural drying, obtain shale oil 301kg, its shale oil rate of recovery is 87.7%, the rate of recovery improves 19.6%, record alkane in shale oil and be increased to 47.12% by 40.34%.
Embodiment 4:
Get somewhere, Guangdong oil shale 10t, oil content is 7.25%, takes manganese oxide 18kg and cobalt oxide 15kg, adds 1+1 sulfuric acid gradually to all dissolving.Then 0.2kg OPEO is added, add water to 340kg, be mixed with the aqueous solution, with the oil shale surface of atomizers spray at granularity <75mm, stir oil shale during sprinkling and make its catalyzed agent solution complete wetting, infiltrate 2.5 hours, Fushun stove carbonization decomposition oil shale is utilized after natural drying, obtain shale oil 638kg, its shale oil rate of recovery is 88.0%, and the rate of recovery improves 17.1%.
Claims (4)
1. extract a catalyst for shale oil for oil shale, it is characterized in that, be mixed by weight by divalence cobalt-manganese salt, water and surfactant, divalence cobalt-manganese salt: water: surfactant is 1:10 ~ 100:0.001 ~ 0.009.
2. according to the catalyst extracting shale oil for oil shale according to claim 1, it is characterized in that, described divalence cobalt-manganese salt is the sulfate of divalence cobalt manganese, hydrochloride or nitrate, or divalence cobalt and manganese oxide is dissolved in the salting liquid of sulfuric acid, hydrochloric acid or nitric acid gained.
3., according to the catalyst extracting shale oil for oil shale according to claim 1, it is characterized in that, described surfactant is dodecyl sodium sulfate, neopelex, OPEO or polyethenoxy ether sodium sulfate.
4. extract a using method for the catalyst of shale oil for oil shale, it is characterized in that, comprise the following steps:
A. oil shale is crushed to <75mm;
B. by weight, catalyst: oil shale is 1:100 ~ 1000, is evenly sprayed at the surface of the oil shale after fragmentation or is immersed in catalyst solution by oil shale, soaking 2-3 hours by catalyst;
Described catalyst is by divalence cobalt-manganese salt: water: surfactant is 1:10 ~ 100:0.001 ~ 0.009;
Described divalence cobalt-manganese salt is the sulfate of divalence cobalt manganese, hydrochloride or nitrate, or divalence cobalt and manganese oxide is dissolved in the salting liquid of sulfuric acid, hydrochloric acid or nitric acid gained;
Described surfactant is dodecyl sodium sulfate, neopelex, OPEO or polyethenoxy ether sodium sulfate;
C. natural drying or force drying;
D. shale oil is produced by cracking process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103878031B (en) * | 2014-04-11 | 2015-11-04 | 西安建筑科技大学 | A kind of oil shale pyrolysis Catalysts and its preparation method and using method |
| CN103952171B (en) * | 2014-05-21 | 2015-06-24 | 抚顺矿业集团有限责任公司 | Oil-clay separation technique for shale |
| CN106433605B (en) * | 2015-08-04 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of oil shale in-situ increases hole activating treatment agent and preparation method thereof |
| CN106753503A (en) * | 2016-12-03 | 2017-05-31 | 吉林大学 | A kind of method that oil shale in-situ catalytic oxidation extracts shale oil gas |
| CN108435154A (en) * | 2017-02-16 | 2018-08-24 | 中国石油化工股份有限公司 | A kind of oil shale in-situ exploitation catalyst and its application method |
| CN109736762A (en) * | 2019-03-22 | 2019-05-10 | 吉林大学 | A kind of method that oil shale in-situ catalytic oxidation extracts shale oil gas |
| CN117166976A (en) * | 2023-09-14 | 2023-12-05 | 东北石油大学 | Oil shale fireflood in-situ catalytic combustion method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786115A (en) * | 2005-11-30 | 2006-06-14 | 曹志德 | Catalyst for producing light fuel oil using oily rock as raw material and its method |
| CN101962559A (en) * | 2010-11-05 | 2011-02-02 | 曹志德 | Method for preparing light fuel oil by using oil shale ore |
| CN102635342A (en) * | 2012-04-10 | 2012-08-15 | 中国海洋石油总公司 | Thermo-chemical oil extraction method of offshore thickened oil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786115A (en) * | 2005-11-30 | 2006-06-14 | 曹志德 | Catalyst for producing light fuel oil using oily rock as raw material and its method |
| CN101962559A (en) * | 2010-11-05 | 2011-02-02 | 曹志德 | Method for preparing light fuel oil by using oil shale ore |
| CN102635342A (en) * | 2012-04-10 | 2012-08-15 | 中国海洋石油总公司 | Thermo-chemical oil extraction method of offshore thickened oil |
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