CN103242882B - Method for producing oil by using co-liquefaction of cotton stalks and coal without adding catalyst - Google Patents

Abstract

The invention discloses a method for performing co-liquefaction of cotton stalks and coal without adding a catalyst. The method comprises the following steps of: pulverizing raw materials of the cotton stalks and coal powder in a mass proportion of 2 to 1 and adding into a kettle body for high-pressure reaction; adding a solvent tetrahydrofuran solution in a mass proportion that the solvent to the raw materials is 1.75 to 1 and sealing the kettle body; introducing hydrogen into the kettle body until the pressure in the kettle is 3MPa; opening a heating furnace to heat; opening a stirrer in the high-pressure reaction kettle to stir in a velocity of 250r/min for 45 minutes to obtain a reaction liquid; exhausting the air in the kettle body; taking out the reaction liquid and extracting the reaction liquid by using a normal hexane solution to obtain oil; drying the extracted solid product and extracting the solid product by using the tetrahydrofuran solution to obtain sparse asphalt; drying the extracted solid product and extracting the solid product by using the tetrahydrofuran solution to obtain former sparse asphalt; drying the extracted solid product to residue slag during liquefaction; and obtaining oil productivity in the process through an equation of oil productivity plus sparse asphalt yield plus former sparse asphalt yield.

Description

A kind of method of not adding catalyzer cotton stalk and coal co grinding method liquefaction

Technical field

The present invention relates to a kind of method of not adding catalyzer cotton stalk and coal co grinding method liquefaction.

Background technology

Enter the 1980s, the problem of environmental pollution that facing mankind the day by day exhausted awkward situation of the fossil energy such as oil, Sweet natural gas and caused owing to using fossil energy in a large number.As a kind of Nonrenewable energy resources, fossil energy is exploited on a large scale under the ever-increasing energy demand of people, thus causes its reserves to reduce rapidly and exhaustion at last.In this case, people are in the urgent need to searching out the replacer of fossil energy, and biomass, coal can be undoubtedly the contenders of this position.

First biomass are often referred to the various materials stemming from plant, are mainly each kind of plant, trees and farm crop, also comprise domestic waste, marine alga and excrement of animals etc.Biomass energy is a kind of renewable energy source, need expend millions of year just obtainable Nonrenewable energy resources this relative to fossil energy, this former unrivaled advantage that it possesses " renewable "---can regenerate within a short period of time--.In addition, derive from the carbon dioxide in air due to the carbon in biomass, so the use of biomass energy can not cause the increase of carbon dioxide total amount in atmospheric layer, greatly reduce the pollution to environment.Based on above reason, the exploitation of biomass energy become the focus of people's research.

In order to efficiency utilization biomass energy, first must carry out conversion to biomass and make it become high heating value, tractable biomass fuel.China is second-biggest-in-the-world energy consumption state, and energy resource supply deficiency has had a strong impact on China's expanding economy, and China is again large agricultural country simultaneously, and biomass resource is very abundant.Wherein, Xinjiang biomass resource enriches as cotton stalk, shell equal yield line, is often only sown areas of cotton and just reaches 1,864 ten thousand mu, but a large amount of cotton stalks produced do not obtain the utilization of sufficient high-qualityization except making domestic fuel.Develop biomass energy and not only can be the energy and the power that Sustainable development provides abundance, also can preserve the ecological environment.

Biomass resource comprises the waste etc. of wooden woods and timber waste, farm crop and their byproduct, urban solid garbage, animal waste, food processing process waste and waterplant and algae, is generally divided into 3 classes: rubbish, the forest reserves and energy crop.Wood Adhesives from Biomass can produce the energy of various ways, as generating, heat supply, provides heat etc. as automobile fuel with for industrial equipments.The transformation technology that utilizes of biomass can be divided into 4 large classes: Direct-Combustion Technology, thermochemical study technology, biochemical conversion technology, curing molding technology.Thermochemical study technology can be divided into again: gasification, pyrolysis, supercritical extraction and Direct liquefaction technology etc.The major way focusing at present biomass is on a large scale pyrolytic gasification method, but its exist the gas heating value that gasification produces low, not easily store and carry, small-scale power generation high in cost of production problem.Biomass fast pyrolysis produces the cutting edge technology that oil is biomass energy research and development in the world at present, but this technology is high to equipment requirements, and reaction conditions is severe should.Compared with rapidly pyrolysing and liquefying technology, the reaction conditions of biomass direct liquefaction and high-pressure liquefaction is relatively gentle, relatively low to equipment requirements, is easy to commercial scale production, so as one of biomass resource efficiency utilization approach.Biomass high-pressure liquefaction transformation technology comes into one's own day by day, becomes one of hot subject of numerous scholar's research.

Its dant is the SOLID ORGANIC combustible product being changed through complicated biological chemistry, physical chemistry and geochemistry process by archaeophyte and generate.Coal can be divided into " humolith " and " sapropelinite " two large class by Coal-forming Plants, the coal generated by higher plant becomes sapropelinite.China and even in the world reserves are large, widespread coal mainly humolith, and general said coal mainly also refers to humolith, and coalification course comprises ulmification stage and coalification stage, the latter have can be divided into into diagenesis and rotten two stage by stage.The coal-forming theory of having built consensus is thought: first Coal-forming Plants changes peat into, and then can change brown coal, sub-bituminous coal, bituminous coal and hard coal successively into or suspend at certain one-phase, and whole process can be described as stage of coalification.Metamorphic grade by brown coal is called " degree of coalification ".

Coal direct liquefaction is one of important technology alleviating China's oil shortage, and at present, deified group is building seat of honour megaton Showcase Production Line.Coal and the circulating solvent hydrogenation liquefaction reaction kinetics under high pressure, higher temperatures is one of key scientific problems of Direct liquefaction technology, becomes the emphasis that relevant investigator both at home and abroad pays close attention to.Some investigators adopt tetraline to be solvent, different catalysts is utilized to be studied the hydrogenation liquefaction mechanism of coal and kinetics, if Robert etc. is by test the direct liquefaction of 69 kinds of high-volatile bituminous coals, proposes coal and generate preasphaltene and asphaltene, preasphaltene and asphaltene and then generate simple consecutive reaction path that is oily and gaseous product; Japan once adopted gelatin liquefaction circulating solvent to carry out the research of kinetics aspect, as Akira KIDOGUCHI etc. adopts 55cm ³autoclave has carried out the dynamics research of hydrogenation liquefaction initial reaction stage to Australian Wandoan coal and Indonesia Tanitoharum coal, think and coal can be divided into rapid conversion component by liquefaction character, transform at a slow speed component and do not transform component, wherein rapid conversion component can be converted into preasphaltene, asphaltene, oil and gaseous product, transform at a slow speed component and be only converted into preasphaltene and asphaltene, and obtain each reaction rate constant by experiment; Onozaki etc. have carried out liquefaction kinetics research on the NEDOL Chinese style device of 150t/d, propose more complicated reaction network.Much research shows, Coal rank is different with the liquefaction kinetics behavior of differential responses condition.

Well-known oil as energy reserves resource comparatively coal and biomass to lack, and skewness, contradiction between oil supply and demand becomes increasingly conspicuous.The rich coal of China, rich biomass, this resources characteristic oil-poor, determine energy development inevitable based on coal and biomass, for a long time, coal accounts for more than 70% in the energy consumption structure of China always.According to prediction: the year two thousand twenty, China will reach 50% to the dependency degree of Imported oil, and the year two thousand thirty will reach 74%.As can be seen here, find a kind of resource that can replace oil, coal becomes the first selection.Development of Coal and biomass-making oil tech and relevant chemical industry, realize with coal and biomass generation oil, have important practical significance and long-range historic significance, it will be solve China's oil shortage of resources, balance energy structure, ensures the grand strategy behave of energy security and the continuous steady progression of national economy spy.Biomass, coal jointly liquefy and just to refer to the coal of solid and biomass in some ratios, by the method for chemical process, make it be converted into the product such as liquid fuel, industrial chemicals.

Technology on High-pressure Liquefaction of Biomass refers to and carry out to biomass the technology that liquefaction reaction produces liquid product under higher pressure, certain temperature and the existent condition such as solvent, catalyzer.And the Direct liquefaction technology of coal refers to that coal is under suitable temperature and pressure, catalytic hydrocracking hot tearing, solvent, extraction, non-catalytic cracking etc. become liquid hydrocarbon, generate a small amount of carburet hydrogen, deviate from the heteroatomic deep conversion processes such as nitrogen content of coal, oxygen and sulphur.

Summary of the invention

The object of this invention is to provide a kind of this autoclave that adopts by the method for cotton stalk and coal co grinding method liquefaction.

In order to achieve the above object, the present invention adopts following scheme:

Do not add catalyzer by a method for cotton stalk and coal co grinding method, it is characterized in that comprising the following steps:

A, by raw material cotton stalk, coal dust by 2: 1 mass ratio pulverize after add the kettle of reaction under high pressure, by solvent: raw material=1.75: the mass ratio of 1 adds solvents tetrahydrofurane solution, is then sealed by kettle;

B, to sealing after kettle in be filled with hydrogen, until kettle internal pressure is 3MPa, and opens process furnace and adjust the temperature to 380 DEG C and heat, the agitator opened in autoclave regulates and stirs speed and stirs to 250r/min, reaction 45min, obtains reaction solution;

C, by after gas emptying in kettle, take out described reaction solution hexane solution and extract, obtain oily;

D, by extraction after solid product carry out drying treatment, then adopt toluene solution extraction, obtain pitch rare;

E, by extraction after solid product carry out drying treatment, then adopt tetrahydrofuran solution extraction, obtain front pitch rare;

Solid product after F, extraction carries out drying treatment and obtains liquefaction process residue;

G, the rare productive rate of oily productive rate+pitch+rare productive rate of front pitch obtain the oily productive rate of this process.

The optimum process condition of the method for cotton stalk of the present invention and coal co grinding method liquefaction is: temperature of reaction is 380 DEG C, reaction pressure is 3MPa, stir speed (S.S.) is 250r/min, broad dose (g)/raw material (g) than be 1.75, the reaction times is 45min, coal (g)/cotton stalk (g) is 1: 2, under these processing condition, gained oil productive rate is 65%.

In order to determine best liquefaction condition in the present invention, do following test:

1, horizontal factor table

(1) reaction times, temperature of reaction, solvent/raw material ratio, coal/cotton stalk is investigated than these four factors to the impact of liquid yield; (2) impact on liquid yield in above-mentioned four factors is found out; (3) processing condition when determining that oily productive rate is the highest.

Table 1 response variable and factor

2, orthogonal

With cotton stalk and coal for raw material, by L ₉3 ⁴orthogonal table carries out 4 factor 3 level experiments.In table 3-2, A factor represents temperature of reaction, and level 1 is 380 DEG C, and level 2 is 420 DEG C, and level 3 is 460 DEG C; B factor represents molten/raw materials quality ratio, and level 1 is 1.75, and level 2 is 2.25, and level 3 is 2.75; C factor represents the reaction times, and level 1 is 45min, and level 2 is 60min, and level 3 is 75min; D factor represents coal/cotton stalk mass ratio, and level 1 is 1: 1, and level 2 is 1: 2, and level 3 is 2: 1

Table 2 orthogonal table

3 interpretations

After finishing experiment according to orthogonal table, done individual calculating to the data obtained, calculation result is as shown in table 3:

The product analysis of table 3 post liquefaction

In the analysis of table 3 post liquefaction product, oily productive rate, asphaltene productive rate, preasphaltene productive rate, gas yield, transformation efficiency, slag productive rate and liquid yield calculate according to formula below:

First the m in table ₀₀, m ₀, m ₁, m ₂, m ₃represent respectively: m ₀₀comprise the quality conjunction of cotton, extractor, cellulose thimble, m ₀the quality of cotton before being catalysis, extractor, cellulose thimble and product liquid, m ₁that amount do not allowed by normal hexane, m ₂that amount do not allowed by toluene, m ₃that tetrahydrofuran (THF) does not allow amount.

1 oily productive rate:

Wherein solvent quality:

The quality of solvent quality=(solvent/raw material) × raw material

2. asphaltene productive rate:

3 preasphaltene productive rates:

4 slag productive rates:

5 transformation efficiencys.

η _corn＝100-η _res

6 liquid yields.

η _liq＝η _ell+η _as+η _pa

7. gas yield:

η _gas＝η _corn-η _liq

4 conclusions

Individual analysis is done to nine groups of orthogonal tests, has calculated K ₁, K ₂, K ₃, k ₁, k ₂, k ₃, R value, have found best liquefaction condition, calculation result is as shown in table 4:

Table 4 orthogonal experiments and analysis

According to K ₁, K ₂, K ₃, k ₁, k ₂, k ₃, R value, what affect liquid yield from master to secondary order is: coal g/ cotton stalk (g) > reaction times > temperature of reaction > molten g/ raw material g.

Such result has been calculated: when temperature of reaction is 380 DEG C according to data, reaction pressure is 3MPa, and speed of response is 250r/min, and solvent g/ raw material g ratio is 1.75, reaction times is 45min, and when coal g/ cotton stalk (g) is 1: 2, liquid yield is up to 67.59%.

Embodiment

Below in conjunction with embodiment, the invention will be further described:

Embodiment 1

By raw material cotton stalk, coal dust by the kettle adding reaction under high pressure after the mass ratio pulverizing of 2: 1, by solvent: raw material=1.75: the mass ratio of 1 adds solvents tetrahydrofurane solution, is then sealed by kettle;

In the kettle after sealing, be filled with hydrogen, until kettle internal pressure is 3MPa, and opens process furnace and adjust the temperature to 380 DEG C and heat, the agitator opened in autoclave regulates and stirs speed and stirs to 250r/min, reacts 45min, obtains reaction solution;

After gas emptying in kettle, take out described reaction solution hexane solution and extract, obtain oily;

Solid product after extraction is carried out drying treatment, then adopts toluene solution extraction, obtain pitch rare;

Solid product after extraction is carried out drying treatment, then adopts tetrahydrofuran solution extraction, obtain front pitch rare;

Solid product after extraction carries out drying treatment and obtains liquefaction process residue;

Oil productive rate+pitch rare productive rate+rare productive rate of front pitch obtains the oily productive rate of this process.

The optimum process condition of the method for cotton stalk of the present invention and coal co grinding method liquefaction is: temperature of reaction is 380 DEG C, reaction pressure is 3MPa, stir speed (S.S.) is 250r/min, broad dose (g)/raw material (g) than be 1.75, the reaction times is 45min, coal (g)/cotton stalk (g) is 1: 2, under these processing condition, gained oil productive rate is 65%.

Claims (1)

1. do not add a method for catalyzer cotton stalk and coal co grinding method liquefaction, it is characterized in that comprising the following steps:

By raw material cotton stalk, coal dust by the kettle adding reaction under high pressure after the mass ratio pulverizing of 2: 1, by solvent: raw material=1.75: the mass ratio of 1 adds solvents tetrahydrofurane solution, is then sealed by kettle;

In the kettle after sealing, be filled with hydrogen, until kettle internal pressure is 3MPa, and opens process furnace and adjust the temperature to 380 DEG C and heat, the agitator opened in autoclave regulates and stirs speed and stirs to 250r/min, reacts 45min, obtains reaction solution;

After gas emptying in kettle, take out described reaction solution hexane solution and extract, obtain oily;

Solid product after extraction is carried out drying treatment, then adopts toluene solution extraction, obtain pitch rare;

Solid product after extraction is carried out drying treatment, then adopts tetrahydrofuran solution extraction, obtain front pitch rare;

Solid product after extraction carries out drying treatment and obtains liquefaction process residue;

Oil productive rate+pitch rare productive rate+rare productive rate of front pitch obtains the liquid yield of this process; Gained liquid yield is 65%.