CN103333043B - Method for preparing acetylene by cracking waste grease with thermal plasma - Google Patents
Method for preparing acetylene by cracking waste grease with thermal plasma Download PDFInfo
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- CN103333043B CN103333043B CN201310245928.1A CN201310245928A CN103333043B CN 103333043 B CN103333043 B CN 103333043B CN 201310245928 A CN201310245928 A CN 201310245928A CN 103333043 B CN103333043 B CN 103333043B
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Abstract
The invention discloses a method for preparing acetylene by cracking waste grease with thermal plasma. The method comprises the following steps of: introducing a working gas to a plasma generator, and forming thermal plasma jet after arcing; and filtering and atomizing the waste grease, mixing the waste grease with a delivered gas, introducing the mixture to the thermal plasma jet in the plasma generator, performing millisecond cracking reaction, and quenching with a cooling medium to obtain cracked gas containing acetylene. The working gas is one or more of hydrogen, argon and nitrogen; the delivered gas is one or more of hydrogen, argon and nitrogen, and can be the same as or different from the working gas; and the cooling medium is one or more of water, hydrogen and waste grease serving as raw materials. According to the method, the waste grease is used as a raw material, so that high value-added utilization of the waste grease is realized, and environmental pollution is reduced; and the method is short in process flow, environment-friendly, economic, efficient, high in utilization rate of the raw materials and high in yield of the acetylene product.
Description
Technical field
The present invention relates to chemical industry synthesis field, particularly relate to a kind of method that thermal plasma cracking waste grease prepares acetylene.
Background technology
A maximum part for waste grease consists of recycled wood materials, can produce a large amount of recycled wood materials in the process for processing such as edible oil, meat and use procedure.For edible oil, the year consumption of the various edible oil of China is 3,000 ten thousand tons, and optimum rate of utilization is by 85%, and the sewer oil that China's catering trade produces every year is up to 2,250,000 tons.In addition, a large amount of discarded commercial greases can be produced in Industrial processes, as waste lubricating oil, machine oil etc.These waste greases not only cause serious environmental pollution, and easily cause various social concern.
Owing to there is no the system setting up sound waste grease recycling, a large amount of waste greases that China every day produces only have and are sent to chemical plant on a small quantity and carry out recycling process, and a large amount of waste greases enters flowing field by illegal channels, even after processing is refined, again flow into food products market, go on the dining table of people, to the healthy and safe formation significant damage of the people.Therefore, accelerate the comprehensive utilization of waste grease imperative.
From current present status in China, following three approach is mainly to the regeneration of waste grease: one is simply process purification, directly as industrial greases such as low-grade leather fats; Two is the process that are hydrolyzed, and produces industrial oleic acid, lipid acid etc.; Three is by alcoholysis process, preparation biofuel.Latter two method belongs to the deep processing of waste grease, good in economic efficiency, fundamentally can solve the problem that waste grease flows into food products market again.Approach two is first hydrolyzed to waste grease, produce lipid acid, be separated again and produce oleic acid, linolic acid and stearic acid, although economic benefit is higher, but use sulfuric acid in production process, a large amount of sour waters can be produced, environment is worked the mischief, and need in producing to use high pressure stainless steel equipment, fund input is huge.It is a popular direction in recent years that approach three prepares biofuel by alcoholysis, has great significance to China's energy development.But because the degree of oxidation of waste grease is different, component difference is comparatively large, need to carry out complicated pre-treatment to adapt to the requirement of biofuel technology of preparing to raw material; And a large amount of glycerine produced in preparation process are underutilized, these all hinder further developing of Biodiesel.
Acetylene is important basic organic chemical raw material, is referred to as " mother of organic chemical industry ", has broad application prospects.The commercial run producing acetylene mainly contains calcium carbide route, methane portion oxidation method and methane electrocracking method, and wherein calcium carbide route prepares acetylene industry maturation, accounts for absolute ratio in the industrial production, but can produce a large amount of CO in process of production
2with Ca (OH)
2in industrial gaseous waste and waste material, very big to the pollution of environment, and energy consumption is higher.
Thermal plasma cracking process prepares acetylene, and be the new technology of an environmental protection, economical and efficient, whole scission reaction can complete within the time of 10ms, provides a new approach for preparing acetylene.As the device and method that patent document discloses a kind of producing acetylene by hydrogen direct current arc plasma cracking coal that publication number is CN101734995A, hydrogen, coal dust is comprised the steps: to send in plasma reactor, quencher chilling is entered after reaction, enter cyclonic separator again and carry out gas, solid pre-separation, its gas fraction enters water washing dedust tower and takes off dirt, after deliver to compressor by booster fan and compress, and then enter that pressure-swing absorber carries out adsorbing, concentrate, again enter compressor from pressure-swing absorber gas out simultaneously and deliver to adsorption tower and extract hydrogen; The solid dust separated through cyclonic separator and water washing dedust tower and water form solution, and carry out liquid with ceramic membrane device, to be admittedly separated, solid dust delivers to power plant as raw material, and water is squeezed in water wash column and carried out recycling.Publication number be CN1552680A patent document discloses a kind of method for preparing acetylene by hot plasma cracking methane containing gas, be plasma jet with plasma generator by argon gas or nitrogen or hydrogen gas ionizes, form hot environment in the reactor; Unstripped gas diffuser is symmetrical in opposite directions multiple tracks air inlet ring, and unstripped gas enters reactor through air inlet ring spray, mixes with the plasma jet running through air inlet ring, rapidly fully soaking; Reactor used is chorate reactor, and gas mixture is restrained in reactor, makes the temperature in reactor keep stable; Refrigerating unit used is pneumatic cooling expansion chamber, is combined with reactor, splitting gas in expansion chamber by chilling.
Summary of the invention
The invention provides a kind of method that thermal plasma cracking waste grease prepares acetylene, be raw material with waste grease, realize the high value added utilization of waste grease, reduce environmental pollution, solve the problem that waste grease flows into food products market; The technical process of the method is short, without the need to catalyzer, environmental friendliness, economical and efficient, and raw material availability is high, the yield of product acetylene is higher.
Thermal plasma cracking waste grease prepares a method for acetylene, comprises the steps:
(1) working gas passes into plasma generator, after the starting the arc, form jet;
(2) waste grease after filtration, atomization, enter after mix with delivering gas in the jet of plasma generator, generation Millisecond scission reaction;
(3) step (2) gained cleavage reaction product is after heat-eliminating medium quenching, obtains, containing acetylene splitting gas, obtaining acetylene after separation.
Described working gas is one or more in hydrogen, argon gas, nitrogen, as preferably, described working gas is one or both in hydrogen, argon gas, the more preferably gas mixture of hydrogen and argon gas, wherein, the content of hydrogen is 30% ~ 100% of gas mixture total mass.In working gas, the existence of hydrogen has material impact for the yield of acetylene, and major cause is: the existence of (1) hydrogen inhibits the decomposition of product acetylene, makes balanced reaction move to the direction generating acetylene simultaneously; (2) there is the hydrogen of atomic state or excited state in plasma body as intermediate, during hydrogen concentration height, in During Quenching, be conducive to CH or C
2h free radical and H composition generation acetylene, thus the content improving acetylene in splitting gas further.
As preferably, the temperature of described jet is 1800K ~ 3500K.When jet temperature is higher than 1800K, the free energy of formation of acetylene starts to be less than other hydrocarbon compound such as methane, ethane, becomes the most stable hydrocarbon molecule.When jet temperature is lower than 1800K, acetylene yield significantly declines, and starts to occur a large amount of solid carbons in system, and this is other component be greater than due to the free energy of formation of now acetylene in system, and Auto-decomposition becomes solid carbon and hydrogen.Jet temperature at the end of scission reaction and the starting temperature of quenching, when jet temperature is too high, during higher than 3500K, will produce a large amount of gaseous carbons in system, and then reduce the productive rate of acetylene.
Described delivering gas is one or more in hydrogen, argon gas, nitrogen, can be identical or different with working gas; The effect of delivering gas is transported in plasma generator by the waste grease of atomization, and with jet contact heat transfer.
The liquid debris of described waste grease to be main component be lipid acid, glycerin fatty acid ester or hydro carbons.As preferably, waste grease is acidification oil, waste cooking oil, sewer oil, expired edible oil, animal tallow, waste lubrication oil or discarded machine oil.
Through atomization process before described waste grease reaction, as preferably, described waste grease forms misty liquid droplets through nozzle, can when mix with jet, increases and the contact area of jet, fully conducts heat.
As preferably, described waste grease enters the high-temperature zone of thermal plasma, and described high-temperature zone is that described quenching device is quencher from the region that thermal plasma is formed until before quenching device.
The mode that described waste grease enters the high-temperature zone of thermal plasma is: after electric arc, enter jet or enter from the side of jet, as preferably, described mode of entrance for enter jet after electric arc again, which can ensure that raw material mixes with thermal plasma evenly.
Acetylene is as the product of plasma pyrolysis waste grease, and its thermodynamic stability determines product gas needs quenching, is at high temperature decomposed into carbon and hydrogen to prevent acetylene.As preferably, described is greater than 10 containing acetylene splitting gas Quenching Rate
7k/s, after quenching, temperature is lower than 600K; Further preferably, described Quenching Rate is greater than 10
8k/s, after quenching, temperature is lower than 350K.Quenching Rate has a significant impact the productive rate of acetylene in splitting gas, and when Quenching Rate is enough large, the acetylene that cracking produces can be retained to greatest extent; If Quenching Rate is too low, then the acetylene produced at high temperature can resolve into rapidly solid carbon and hydrogen, reduces the productive rate of acetylene.
The direction that described heat-eliminating medium sprays into quencher is for radial and tangential, and as preferably, described heat-eliminating medium sprays into the direction of quencher for radial, and heat-eliminating medium sprays into can better mix with splitting gas from radial direction, and cooling performance is better.
Described heat-eliminating medium is one or more in water, hydrogen, raw material waste grease.As preferably, described heat-eliminating medium is one or both in water, raw material waste grease.Adopt water heat-eliminating medium maximizing acetylene yield the most, and fully transform and utilize waste grease; Adopt raw material waste grease as heat-eliminating medium, not only can regulate the C/H mol ratio of gas-phase product, affect the yield of product acetylene, and heat remaining in jet can be made full use of, thus reduce the energy expenditure preparing acetylene.
As preferably, described splitting gas separation method is absorption extraction.
A kind of thermal plasma cracking of the present invention waste grease prepares the method for acetylene, is raw material, realizes the high value added utilization of waste grease with waste grease, reduces environmental pollution, solves the problem that waste grease flows into food products market.And this reaction is good to the adaptability of raw material, to the composition of waste grease without particular requirement, without the need to carrying out pre-treatment.
Cracking process carries out under the high temperature of the thousands of degree of thermal plasma, the splitting gas that waste grease only can need obtain containing acetylene by the scission reaction of a step Millisecond, and technical process is short, without the need to catalyzer, economical and efficient; And raw material availability is high, the transformation efficiency of waste grease is greater than 95%, and the yield of product acetylene is greater than 70%; Whole process does not produce acidic and alkaline waste water, environmental friendliness.
Embodiment
Embodiment 1
Hydrogen is passed in DC arc plasma generator that power input is 45kW, after the starting the arc, form the jet of more than 3000K.Expired soybean salad oil through ram pump with the speed of 5kg/h through nozzle atomization, the high-temperature zone of reactor is entered after mixing with hydrogen, through Millisecond scission reaction, the splitting gas of generation is passed into quencher, using water as heat-eliminating medium, radial direction passes in quencher and rapidly splitting gas is cooled to 360K, and rate of cooling is 2 × 10
-7k/s, obtains the splitting gas containing acetylene, obtains acetylene after absorption extraction.
Through gas chromatographic detection and analytical calculation, the yield of reaction product acetylene is 72.0%, and the transformation efficiency of waste grease is 99.6%.
Embodiment 2
Hydrogen is passed in DC arc plasma generator that power input is 50kW, after the starting the arc, form the jet of more than 2500K.Water content be 5% sewer oil process after filtration, through ram pump with the speed of 5kg/h through nozzle atomization, the high-temperature zone of reactor is entered after mixing with hydrogen, through Millisecond scission reaction, the splitting gas of generation is passed into quencher, using water as heat-eliminating medium, tangentially pass in quencher and rapidly splitting gas is cooled to 400K, rate of cooling is 2 × 10
-7k/s, obtains the splitting gas containing acetylene, obtains acetylene after absorption extraction.
Through gas chromatographic detection and analytical calculation, the yield of reaction product acetylene is 78.5%, and the transformation efficiency of waste grease is 99.2%.
Embodiment 3
The mixed gas of argon gas and hydrogen is passed in the DC arc plasma generator that power input is 15kW, after the starting the arc, forms the jet of more than 2500K.Waste lubrication oil processes after filtration, through ram pump with the speed of 1.5kg/h through nozzle atomization, the high-temperature zone of reactor is entered after mixing with argon gas, through Millisecond scission reaction, the splitting gas of generation is passed into quencher, using waste lubrication oil and water as heat-eliminating medium, radial direction passes in quencher and rapidly splitting gas is cooled to 400K successively, and rate of cooling is 3 × 10
-7k/s, obtains the splitting gas containing acetylene, obtains acetylene after absorption extraction.
Through gas chromatographic detection and analytical calculation, the productive rate of reaction product acetylene is 70.7%, and the transformation efficiency of waste grease is 98.8%.
Claims (3)
1. thermal plasma cracking waste grease prepares a method for acetylene, it is characterized in that, comprises the steps:
(1) working gas passes into plasma generator, after the starting the arc, form jet;
(2) waste grease after filtration, atomization, enter after mix with delivering gas in the jet of plasma generator, generation Millisecond scission reaction;
(3) step (2) gained cleavage reaction product is after heat-eliminating medium quenching, obtains, containing acetylene splitting gas, obtaining acetylene after separation;
Described working gas is the gas mixture of hydrogen and argon gas, and wherein, the content of hydrogen is 30% ~ 100% of gas mixture total mass;
Described waste grease is acidification oil, waste cooking oil, sewer oil, expired edible oil, animal tallow, waste lubrication oil or discarded machine oil;
Described delivering gas is one or more in hydrogen, argon gas, nitrogen, can be identical or different with working gas;
Described heat-eliminating medium is one or more in water, hydrogen, raw material waste grease;
Described quenching, its Quenching Rate is greater than 10
7k/s, after quenching, temperature is lower than 600K.
2. thermal plasma cracking waste grease as claimed in claim 1 prepares the method for acetylene, and it is characterized in that, the temperature of the jet described in step (1) is 1800K ~ 3500K.
3. thermal plasma cracking waste grease as claimed in claim 1 prepares the method for acetylene, it is characterized in that, the heat-eliminating medium described in step (3) is one or both in water, raw material waste grease.
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| CN201310245928.1A CN103333043B (en) | 2013-06-19 | 2013-06-19 | Method for preparing acetylene by cracking waste grease with thermal plasma |
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| CN201310245928.1A CN103333043B (en) | 2013-06-19 | 2013-06-19 | Method for preparing acetylene by cracking waste grease with thermal plasma |
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| CN103333043A CN103333043A (en) | 2013-10-02 |
| CN103333043B true CN103333043B (en) | 2015-02-04 |
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| US4536603A (en) * | 1983-12-22 | 1985-08-20 | Rockwell International Corporation | Production of acetylene from coal by contact with a combustion gas |
| CN1600758A (en) * | 2003-09-25 | 2005-03-30 | 田原宇 | Technique for producing acetylene from hot plasma of hydrocarbon and equipment |
| CN1235846C (en) * | 2003-12-18 | 2006-01-11 | 四川大学 | Method for preparing acetylene by hot plasma cracking methane containing gas |
| CN103100365B (en) * | 2011-11-11 | 2015-05-13 | 北京低碳清洁能源研究所 | Plasma cracking carbonaceous material reactor system with hollow cathode or double hollow cathodes |
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