CN1043027C - Cracking process for producing hydrogen and sepecial equipment for producing hydrogen - Google Patents
Cracking process for producing hydrogen and sepecial equipment for producing hydrogen Download PDFInfo
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- CN1043027C CN1043027C CN96100965A CN96100965A CN1043027C CN 1043027 C CN1043027 C CN 1043027C CN 96100965 A CN96100965 A CN 96100965A CN 96100965 A CN96100965 A CN 96100965A CN 1043027 C CN1043027 C CN 1043027C
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 179
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- 238000002309 gasification Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
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- 235000014676 Phragmites communis Nutrition 0.000 claims description 10
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- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 claims description 5
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- 230000009471 action Effects 0.000 claims description 3
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- 230000005611 electricity Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
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- 244000089486 Phragmites australis subsp australis Species 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 10
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
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- 238000002485 combustion reaction Methods 0.000 description 24
- 239000003502 gasoline Substances 0.000 description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 18
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
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- 150000002431 hydrogen Chemical class 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
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- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
The present invention relates to a cracking hydrogen making technology. Through the residual heat generated through the exhaust of an engine, unleaded low-sulfur petrol (hydrocarbon) with a boiling point of 40 to 200 DEG C, ammonia and alcohol are used as a cracking hydrogen making raw material. Firstly, a hydrogen making raw material is cracked in a catalytic mode and is converted to hydrogen-rich gas, and then the hydrogen-rich gas and the petrol are activated and evenly mixed in a vortex supersonic device and enter the engine as a fuel to realize the fuel is replaced by hydrogen and is burned. A hydrogen generator specially designed for the practice of the technology has the advantages of compact structure, quick temperature rise speed and low burn-up cost to reach the purpose of saving 14 to 30% of oil, and 30 to 50% of pollutants exhausted by cars are reduced. The purification rate of carbon smoke exhausted by a diesel engine reaches more than 62 percent to conform to the requirement of environmental protection laws and regulations.
Description
The present invention relates to cracking hydrogen production technology, relate in particular to the cracking hydrogen production technology that is widely used in automobile, aircraft, locomotive, steamer oil engine, gas turbine engine, power station, industry, civil boiler etc. and for implementing the custom-designed specific equipment hydrogen generator of this technology.
As everyone knows, the mankind especially reduce the pollution of diesel emission soot particle to atmospheric environment in order to reduce dependence and the minimizing automotive emissions to petroleum resources, all at a kind of new forms of energy that can substitute vapour (bavin) oil of the searching of trying every possible means; " ecology-environmentally friendly vehicle " can appear early.Scientists assert that by exploration and the research of three more than ten years alcohols, Hydrogen Energy and Sweet natural gas (CNG) are to meet the new forms of energy and the renewable energy resources that human ecological environment requires.United Nations and international automobile financial group think that pure hydrogen is the high-tech industry focus and emphasis of 21st century for combustion, and trend of the times is imperative.102-486 of US Congress and 101-566 bill require to gradually reduce the dependence to fossil oil, (U.S.) traffic and transportation system reduces 50% to the dependence of oil in 20 years, and the regulation development is carried hydrogen storage technology (using the methanol recapitalization cracking hydrogen production onboard) with car.And advance the production of gasoline-natural gas vehicle by double fuels simultaneously.
But methyl alcohol toxicity, corrosion and burnup cost height are the Three Difficult Issues in practical the popularization, are difficult in the recent period and the competition of vapour (bavin) field, oil market.Sweet natural gas burnup cost is low, and its oxynitride that discharges pollutants (NOx) and carbon monoxide (CO) only are 1/25 and 1/20 of gasoline car.Capital investment is huge, and the steel cylinder equipment of Sweet natural gas station and 160 standard atmospheric pressures is the obstacle of Sweet natural gas for the combustion technology industrialization always.
Purpose of the present invention is exactly at problems of the prior art, invent a kind of hydrogen generator device, utilize exhaust heat, select for use unleaded low-sulphur oil (hydro carbons), alcohols, ammonium bicarbonate new forms of energy fuel to carry out the technology of hydrogen production from catalytic pyrolysis, in the hope of alleviate, avoid the difficult problem that above-mentioned new forms of energy fuel exists in implementing for the combustion process, realize with hydrogen for combustion.The present invention also aims to simultaneously to provide a kind of compact construction, in light weight, intensity good, heat-up rate is fast, the burnup cost is low, energy-conservation, be beneficial to the specific equipment-hydrogen generator of the realization cracking hydrogen production technology of protection environment.
In order to understand the present invention better, now set forth the work structuring principle of hydrogen generator of the present invention: the present invention utilizes exhaust heat to carry out alcohol, oil, the cracking of ammonium fuel catalytic.Exhaust is entered by the noise elimination mouth of pipe, turn to outside the hush tube 13 discharge machines by middle hush tube 16, carry out noise elimination noise reduction in the passage that exhaust is advanced in sourdine, and the hot cell of gasifying of preheating simultaneously, reaction chamber housing outer wall and perforation tubulation etc., when thermocouple signal transmission in the reaction chamber reaches alcohol (oil) (ammonium) catalytic pyrolysis temperature preset value, the starting of automatic instrument(s) instruction alcohol (oil) (ammonium) pump, alcohol (oil) (ammonium) fuel enters vaporizer shunting gasification via inlet tube, under engine air inlet tube suction suction function, the fuel that has gasified, it is overheated progressively to heat up through perforation tubulation outer wall, and under the effect of vibrating reed, become and activate supersonic fuel gas, pass wire cloth via communicating pipe again, enter reaction chamber.In a single day alcohol (oil) (ammonium) steam contacts and passes catalytic bed with catalyzer, through catalytic pyrolysis, (hydrogen-rich gas, main component are H promptly to be converted into hydrogen
2, CO, CH
4Deng), after cooling in the hydrogen air tank, purification, the voltage stabilizing, last hydrogen rich gas follows pipeline and enters mixing tank and inlet pipe as motor spirit.For strengthening and improving the hydrogen doping combustion efficacy of petrol and diesel oil, mixing tank adopts special vartex ultrasound structure, can make the molecule of gasoline, hydrogen air activate ultrasonicization by wortex device, mixes, thereby has improved the thermo-efficiency and the exhaust gas purification rate of engine.Because alcohol (oil) (ammonium) cracking process is thermo-negative reaction, needs to consume the entrained a large amount of heats of exhaust, reduces exhaust temperature and pressure, thereby further reduces the noise by exhaust produced.When thermocouple signal transmission surpasses alcohol (oil) (ammonium) cracking temperature preset value, automatic instrument(s) instruction bypassing exhaust, avoid overheated for guard catalyst this moment, and high-temperature exhaust air changes by separation panel tracheae 7 and enters outside the direct discharge machine in tailpipe 37 backs.
In order to realize above-mentioned purpose of the present invention, the invention provides following technical scheme:
Utilize engine exhaust heat, at first hydrogen feedstock is carried out catalytic pyrolysis and be converted into hydrogen-rich gas, make hydrogen-rich gas and vapour (bavin) oil be mixed into the cracking hydrogen production technology that engine acts as a fuel then.In cracking hydrogen production specific equipment hydrogen generator of the present invention, adopting boiling point is that 40～200 ℃ of unleaded low-sulphur oil are the cracking hydrogen production raw material, and using stock oil is the prescription of 1 to 1～1.2 weight ratios than water, at nickeliferous 40～60%, platinum palladium 0.05～0.2%, Al
2O
3Under the catalyst action, reach 300～760 ℃, pressure at the hydrogen generator bed temperature and reach and carry out the gasification cracking reaction under 1～4 MPa condition, produce hydrogen-rich gas.Formula optimization employing steam oil ratio (SOR) water is 1 to 1～1.2 weight ratio, adds 5% additive in water.
The another kind of cracking hydrogen production technology of the present invention is to utilize engine exhaust heat, at first hydrogen feedstock is carried out catalytic pyrolysis and is converted into hydrogen-rich gas, makes hydrogen-rich gas and vapour (bavin) oil be mixed into engine and act as a fuel then.In cracking hydrogen production specific equipment hydrogen generator of the present invention, adopting boiling point is that 40～80 ℃ of alcohols are the cracking hydrogen production raw material, and using raw alcohol is the prescription of 1 to 0.1～1.2 weight ratios than water, at CuO, ZnO, MnO
2, Ni, K, Al
2O
3Effect down reaches 160～760 ℃, pressure at the hydrogen generator bed temperature and reaches and carry out the gasification cracking reaction under 0.02～4 MPa condition, produces hydrogen-rich gas.It is 1 to 0.1～1.2 weight ratio than water that formula optimization adopts methyl alcohol or ethanol, adding 5% additive in water.
The another kind of cracking hydrogen production technology of the present invention is to utilize engine exhaust heat, at first hydrogen feedstock is carried out catalytic pyrolysis and is converted into hydrogen-rich gas, makes hydrogen-rich gas and vapour (bavin) oil be mixed into engine and act as a fuel then.In cracking hydrogen production specific equipment hydrogen generator of the present invention, adopting boiling point is that 40～65 ℃ of ammonium bicarbonates are the cracking hydrogen production raw material, and using the material carbon ammonium is the prescription of 1 to 1～1.2 weight ratios than water, at nickeliferous 40～60%, platinum palladium 0.05～0.2%, K, Al
2O
3Under the catalyst action, reach 300～760 ℃, pressure at the hydrogen generator bed temperature and reach and carry out the gasification cracking reaction under 0.02～4 MPa condition, produce hydrogen-rich gas.It is 1 to 1～1.2 weight ratio than water that formula optimization adopts volatile salt or bicarbonate of ammonia, adding 5% additive in water.
The present invention provides in addition to realizing the custom-designed hydrogen generators 1 of above-mentioned three kinds of cracking hydrogen production technologies, and hydrogen generator 1 directly is serially connected on the gas exhaust duct 56 of engine 50, is combined into one with the exhaust snubber of engine.Its internal structure connects into the U-shaped structure by gasified hot cell 10 and reaction chamber 19 through communicating pipe 2, on it gasifies hot cell 10 inwall both sides gas channels a few row's pectination ultrasonic vibration reeds is set.The feeder system of hydrogen generator is by alcohol (water) case 49, valve 43a, and b, pump 36,46, pipeline 28 are formed, and carry the hydrogen-rich gas system to be made up of pipeline 31, air tank 41, valve 44, fuel mixer 48; In order to strengthen the hydrogen doping state of combustion of gasoline, improve efficiency of combustion, fuel mixer adopts custom-designed vortex ultrasound structure.Engine exhaust passage is to follow pipeline 56, through bypassing exhaust valve 42, enters hydrogen generator then, is discharged into atmosphere by pipeline 37.When temperature reaches set(ting)value, by thermopair temperature controller 58 instruction electricity alcohol (water) pump startups,, when temperature surpasses preset value, make bypassing exhaust by thermopair temperature controller 58 electromagnetic valve of instruction to the hydrogen generator feed, follow pipeline 7 and be discharged into atmosphere.In order to reach better effect, a few row's pectination vibrating reeds are set on hydrogen generator internal gas flow passage.The vibrating reed material can adopt stainless steel or steel nickel chrome, thickness 0.2～2.4mm, and vibrational frequency is the 8000-24000 kilocycle.Fuel mixer 48 is the ultrasonic device structures of vortex, and the air outlet is to locate in volute inwall lower edge.
Above-mentioned hydrogen generator provided by the invention can be used on power station, industry, civil boiler, also can be widely used in automobile, aircraft, locomotive, steamer oil engine, the gas turbine engine.Technical scheme of the present invention has following outstanding advantage:
1, the hydrogen generator structure of Shi Yonging is cellular cylindrical or oval, this compact construction, and consumptive material is few, weight saving 50%, loaded catalyst increases by three times, and intensity is good, is heated, conducts heat evenly, and heat-up rate is fast.
2, fuel mixer of the present invention is a dish type rotary ultrasonic mixer structure, mixes, and is convenient to install with existing motor car engine combination, easily realizes the engine underpressure burning, and it is energy-conservation to mix hydrogen; Easily realize engine booster, improve power and improve the tail gas clean-up rate.Do not adopt before the ultrasonic device structure of vortex, when on east wind EQ-140 type gasoline car, implementing alcohol-hydrogen for combustion, when average be 30～50% (weight ratios) for the combustion amount, alcohol-hydrogen is to alternative ratio≤1 of gasoline, and guarantee on the basis of former mechanomotive force, economy, fuel-economizing (energy) 6～18%, the exhaust emissions purification rate limits row's standard to compare with country, carbon monoxide reduces by 30%, and hydrocarbon polymer reduces by 14～30%; Improve the tail gas clean-up rate after adopting the ultrasonic device of vortex: carbon monoxide reduces by 50～80%, and hydrocarbon polymer reduces by 30～50%.
3, the present invention utilizes exhaust heat, draws from the available engine vapor pipe, need not do any change to prior art, install and use all very convenient, bypassing exhaust, catalytic bed constant temperature is by the thermal sensing element automatic control, also can utilize gear mechanical linkage, realize the automatic control of catalytic bed constant temperature.
4, hydrogen-rich gas volume of the present invention is 0～85%, and can be adjustable at random in 0～85% scope, when the no hydrogen feed, can pure gasoline be fuel still, and its performance is identical with former machine.
5, apparatus of the present invention hydrogen generator can adapt to multiple cracking hydrogen production raw material, with existing various generation combustion technology relatively have remarkable economy and practicality.
(1) gasoline water mixing cracking hydrogen production and general oily water mixing (oil in water emulsion) for combustion technology relatively have tangible 14～30% energy-conservation and filth-discharging effects, and have avoided the stratified difficult problem of profit.Gasoline water mixing splitting gas composition of the present invention after testing is: hydrogen 16%, methane 62%, carbon monoxide 0.6%, carbonic acid gas 21.4% wherein also contains 12～18% (this profit steam can enter cylinder with hydrogen-rich gas and participate in burning and cracking again) that last cracked profit steam accounts for charging capacity.Just compare with splitting gas composition and gas component, two kinds of gases all contain high methane gas, but Sweet natural gas lacks hydrogen, does not possess the hydrogen doping combustioncharacteristics of gasoline, and the steel cylinder pressure exerting device of Sweet natural gas station and 160 standard atmospheric pressures is the obstacle of Sweet natural gas for combustion technology practicability always simultaneously.
(2) alcohol (ammonium) cracking hydrogen production has not only solved methyl alcohol toxicity, corrosion and the high Three Difficult Issues of burnup cost that international alcohols exists for combustion technology.And, have better economic results in society by exploitation of automobile and detection.Alcohol splitting gas composition is: hydrogen 64.29%, carbon monoxide 31.61%, methane 1.13%, carbonic acid gas 2.24%, nitrogen 0.62%, oxygen 0.16%.(volatile salt splitting gas composition is: hydrogen 64～67%, carbon monoxide 28%, carbonic acid gas 8%).When implementing the generation combustion with hydrogen-rich gas, when average be 30～50% (weight ratios) for the combustion amount, alcohol (hydrogen) is to alternative ratio≤1 of gasoline, and guarantees on the basis of former mechanomotive force, economy fuel-economizing (energy) 14～30%.
6, help environment protection.The present invention limits row's standard to compare the gasoline exhaust pollutant load with country, and carbon monoxide reduction by 50%, hydrocarbon polymer reduce by 30%, and diesel emission soot particle purification rate is more than 62%.Reach the requirement of environmental regulation technical indicator.
7, since the present invention in the gasification of hydrogen generator the hot cell be provided with a few row's vibrating reeds, play the effect that activates ultrasonicization, thereby the reaction effect of oil (alcohol) (ammonium) cracking hydrogen production be more than doubled.Before being unkitted, the methanol decomposition amount has been adorned after the vibrating reed for per hour 5 kilograms, and the methanol decomposition amount reaches per hour 11.5 kilograms.Lysis efficiency is brought up to more than 95% by 85%.
The invention provides 10 width of cloth accompanying drawings, drawing is described as follows:
Fig. 1 is the structural representation of hydrogen generator of the present invention;
Fig. 2 is the front view of device shown in Figure 1;
Fig. 3 is the vertical view of device shown in Figure 1;
Fig. 4 is the A-A sectional view among Fig. 1;
Fig. 5 is the B-B sectional view among Fig. 2, mainly marks hydrogen generator vibrating reed structure;
Fig. 6 is the C-C sectional view among Fig. 2;
The schematic flow sheet that Fig. 7 hydrogen generator and engine are complementary;
Fig. 8 is a fuel mixer vortex ultrasound structure synoptic diagram of the present invention;
Fig. 9 is the D-D sectional view among Fig. 8;
Figure 10 is the structural representation of mixing tank cover.
The contrast accompanying drawing is set forth embodiments of the invention below, but that content of the present invention is not limited to drawings and Examples is described.
Embodiment 1:
First 1-7 in conjunction with the accompanying drawings illustrates the structure that leaves standstill of hydrogen generator of the present invention.
Hydrogen generator 1, communicating pipe 2, preceding shrouding 3, vapor pipe 4, sleeve pipe 5, perforated pipe 6, shrouding 8 before the separation panel tracheae 7, preheating chamber, sleeve pipe 9, the hot cell 10 of gasifying, shrouding 11 behind the preheating chamber, dividing plate 12, noise elimination tail pipe 13, dividing plate 14,15, middle hush tube 16, shrouding 18 before the dividing plate 17, reactor, reaction chamber 19, sleeve pipe 20, shrouding 21 behind the reactor, reactor perforated pipe 22, flange 23, capping 24, screw 25, thermal cross 26, back shrouding 27, alcohol (oil) (ammonium) fuel inlet pipe 28, alcohol (oil) (ammonium) liquid gasification spreader plate 29, hydrogen-rich gas input aperture 30, hydrogen-rich gas output tube 31, panel opening 32, gasoline pipe 33,34, alcohol (water) feeder sleeve 35, alcohol (water) pump 36, tailpipe 37, hydrogen and air mixer 38, thermopair circuit 39, hydrogen-rich gas pneumatic tube 40, hydrogen-rich gas air tank 41, bypassing exhaust valve 42, feed valve 43a, b, air valve 44, pneumatic thickener 45, oil pump 46, carburettor 47, mixing tank 48, alcohol (water) case 49, engine 50, vibrating reed 51,52, mixing tank joint 53, wortex device shell 54, wortex device inwall 55, exhaust-gas receiver 56, wortex device cavity 57, thermopair temperature controller 58, wortex device outlet 59.
East wind gasoline car EQ-140 type production operation is carried specified 5 tons, plateau tertiary road face in fact.Utilize the hydrogen producer-hydrogen generator of the invention described above to implement alcohol-hydrogen for combustion, for combustion amount 50%, fuel-economizing (energy) 14～25%.The cracking hydrogen production composition of raw materials that adopts is: 64 kilograms of methyl alcohol (or ethanol), and 30 kilograms in water, 6 kilograms of additives (being that volatile salt, bicarbonate of ammonia or the yellow soda ash of gross weight 3～5% is additive with weight preferably) are used for following cracking hydrogen production technology:
Automobile under steam, when thermocouple signal catalyzer bed temperature reaches 280 ℃ in the hydrogen generator 1, circuit is connected methanol pump 36 and is started, this moment, oil circuit cut off, valve 43b is in closing condition, the aqueous methanol of alcohol in the case 49 enters hydrogen generator by the road and carries out preheating, gasification, overheated cracking hydrogen production process, and the hydrogen-rich gas of generation enters inlet pipe after by memory 41 voltage stabilizings, cooling, purification and enters cylinder as motor spirit with gasoline from carburettor 47 after the ultrasonic device of vortex activates uniform mixing.
Above-mentioned cracking hydrogen production processing condition are: 300 ℃ of temperature, and pressure 0.12 MPa, catalyzer is with containing Cu-Zn, Ni, K, Al
2O
3Catalyzer.
Dissociated methanol gas composition after above-mentioned technology cracking is: hydrogen 69.9%, carbon monoxide 19.9%, methane 0.2%, carbonic acid gas 10.0%, cleavage rate are 90.03%.
Tail gas is detected as and is divided into: carbon monoxide 0.1% (GB 3842-83 standard≤5%), hydrocarbon polymer (HC) 1200ppm (GB3842-83 standard≤2500ppm), oxynitride (NOx) trace.
Embodiment 2:
East wind gasoline car EQ-140 type production operation, the engine pedestal checking utilizes the hydrogen producer of the present invention-hydrogen generator among the embodiment 1 to implement gasoline water mixing cracking hydrogen production, for combustion amount 50%, fuel-economizing (energy) 14～30%.The hydrogen manufacturing prescription that adopts is: 45 kilograms in gasoline, and 55 kilograms in water, 5 kilograms of additives (being that volatile salt, bicarbonate of ammonia or the yellow soda ash of gross weight 3～5% is additive with weight preferably) are used for following process for making hydrogen:
With embodiment 1 with, different is, and what to deposit in the pure case 49 is water, valve 43a and valve 43b open simultaneously.
Above-mentioned process for making hydrogen condition is: 600 ℃ of temperature, and pressure 1.0 MPas, catalyzer is with nickeliferous 40-60%, platinum palladium 0.05-0.2%, K, Al
2O
3
Composition after above-mentioned technology cracking is: hydrogen 16%, carbon monoxide 0.6%, methane 62%, carbonic acid gas 21.4%, cleavage rate are 82-88%.
Environmental protection tests: carbon monoxide 1.5% (GB 3842-83 standard≤5%), hydrocarbon polymer (HC) 800ppm (GB 3842-83 standard≤2500ppm), oxynitride (NOx) trace.
Embodiment 3:
East wind diesel engine (supercharging), platform experiment utilizes hydrogen producer of the present invention in the foregoing description 1-hydrogen generator to implement alcohol-hydrogen for combustion, on the basis that guarantees former mechanomotive force, economy, measures 50% fuel-economizing (energy) 14～30% for combustion.The cracking hydrogen production composition of raw materials that adopts is: 45 kilograms of methyl alcohol, and 5 kilograms of 55 kilograms of additives of water (being that volatile salt, bicarbonate of ammonia or the yellow soda ash of gross weight 3～5% is additive with weight preferably) are used for following cracking hydrogen production technology:
Automobile is under steam when thermocouple signal catalyzer bed temperature reaches 280 ℃ in the hydrogen generator 1, circuit is connected methanol pump 36 and is started, this moment, oil circuit cut off, valve 43b is in closing condition, the aqueous methanol of alcohol in the case 49 enters hydrogen generator by the road and carries out preheating, gasification, overheated cracking hydrogen production process, and the hydrogen-rich gas of generation enters inlet pipe after by memory 41 voltage stabilizings, cooling, purification and is mixed in the ultrasonic device of vortex with air from empty filter and enters cylinder as motor spirit.
Above-mentioned cracking hydrogen production processing condition are: 300 ℃ of temperature, and pressure 0.12 MPa, catalyzer is with containing Cu, Zn, Ni, K, Al
2O
3
Dissociated methanol gas composition after above-mentioned technology cracking is: hydrogen 72%, carbon monoxide 2.4%, methane 3.0%, carbonic acid gas 22.6%, cleavage rate are more than 99%.
Tail gas is detected as and is divided into: the soot particle purification rate is more than 62%, reaches the requirement of environmental regulation technical indicator.
Embodiment 4:
East wind gasoline car EQ-140 type production operation is carried specified 5 tons, plateau tertiary road face in fact.Utilize the hydrogen producer-hydrogen generator of the invention described above to implement ammonium bicarbonate hydrogen manufacturing for combustion, for combustion amount 50%, fuel-economizing (energy) 12～25%.The cracking hydrogen production composition of raw materials that adopts is: 45 kilograms of volatile salts, and 55 kilograms in water is used for following cracking hydrogen production technology:
Automobile under steam, when thermocouple signal catalyzer bed temperature reaches 280 ℃ in the hydrogen generator 1, circuit is connected ammonium fluid pump 36 and is started, this moment, oil circuit cut off, valve 43b is in closing condition, hydrocarbon ammonium in the carbon ammonium case 49 enters hydrogen generator by the road and carries out preheating, gasification, overheated cracking hydrogen production process, and the hydrogen-rich gas of generation enters inlet pipe after by memory 41 voltage stabilizings, cooling, purification and enters cylinder as motor spirit with the gasoline from carburettor 47 behind the ultrasonic device uniform mixing of vortex.
Above-mentioned carbon ammonium cracking hydrogen production processing condition are: 450 ℃ of temperature, pressure 0.2 MPa, catalyzer Cu, Zn, Ni, K, Al
2O
3
Carbon ammonium splitting gas composition after above-mentioned technology cracking is: hydrogen 64%, carbon monoxide 28%, carbonic acid gas 8%, cleavage rate are more than 99%.
Tail gas is detected as and is divided into: carbon monoxide 0.1% (GB 3842-83 standard≤5%), hydrocarbon polymer (HC) 1200ppm (GB 3842-83 standard≤2500ppm), oxynitride (NOx) trace.
Embodiment 5:
Jiefang brand 141 type automobile productions operation, the engine pedestal checking utilizes the hydrogen producer of the present invention-hydrogen generator among the embodiment 1 to implement the profit cracking hydrogen production for combustion, for combustion amount 52%, fuel-economizing (energy) 18～25%.The cracking hydrogen production prescription that adopts is: 50 kilograms in gasoline, and 60 kilograms in water, 6 kilograms of additives (being that the volatile salt or the yellow soda ash of gross weight 3～5% is additive with weight preferably) are used for following cracking hydrogen production technology:
With embodiment 1 with, different is, and what to deposit in the pure case 49 is water, valve 43a and valve 43b open simultaneously.
Above-mentioned process for making hydrogen condition is: 600 ℃ of temperature, and pressure 1.0 MPas, catalyzer is with nickeliferous 40-60%, platinum palladium 0.05-0.2%, K, Al
2O
3
Composition after above-mentioned technology cracking is: hydrogen 21%, carbon monoxide 0.8%, methane 55%, carbonic acid gas 23.2%, cleavage rate are 82-88%.
Environmental protection tests: carbon monoxide 2.3% (GB 3842-83 standard≤5%), hydrocarbon polymer (HC) 850ppm (GB 3842-83 standard≤2500ppm), oxynitride (NOx) trace.
Claims (9)
1, a kind of cracking hydrogen production technology, utilize engine exhaust heat, at first hydrogen feedstock is carried out catalytic pyrolysis and be converted into hydrogen-rich gas, make hydrogen-rich gas and vapour (bavin) oil be mixed into engine and act as a fuel then, it is characterized in that in cracking hydrogen production specific equipment hydrogen generator, adopting boiling point is that 40～200 ℃ of unleaded low-sulphur oil are the cracking hydrogen production raw material, and using oil ratio water is the prescription of 1 to 1～1.2 weight ratios, at nickeliferous 40～60%, platinum palladium 0.05～0.2% and K, Al
2O
3Under the effect of catalyzer, reach 300～760 ℃, pressure at the hydrogen generator bed temperature and reach and carry out the gasification cracking reaction under 1～4 MPa condition, produce hydrogen-rich gas.
2, according to the described technology of claim 1, it is characterized in that adopting steam oil ratio (SOR) water is 1 to 1～1.2 weight ratio, adds 5% ammonium bicarbonate additive in water.
3, a kind of cracking hydrogen production technology, utilize engine exhaust heat, at first hydrogen feedstock is carried out catalytic pyrolysis and be converted into hydrogen-rich gas, make hydrogen-rich gas and vapour (bavin) oil be mixed into engine and act as a fuel then, it is characterized in that in cracking hydrogen production specific equipment hydrogen generator, adopting boiling point is that 40～80 ℃ of alcohols are the cracking hydrogen production raw material, and using raw alcohol is the prescription of 1 to 0.1～1.2 weight ratios than water, is containing CuO, ZnO, MnO
2, Ni, K, Al
2O
3Under the effect of catalyzer, reach 160～760 ℃, pressure at the hydrogen generator bed temperature and reach and carry out the gasification cracking reaction under 0.02～4 MPa condition, produce hydrogen-rich gas.
4, according to the described technology of claim 3, it is characterized in that adopting alcohol is 1 to 0.1～1.2 weight ratio than water, adding 5% ammonium bicarbonate additive in water.
5, a kind of cracking hydrogen production technology, utilize engine exhaust heat, at first hydrogen feedstock is carried out catalytic pyrolysis and be converted into hydrogen-rich gas, make hydrogen-rich gas and vapour (bavin) oil be mixed into engine and act as a fuel then, it is characterized in that in cracking hydrogen production specific equipment hydrogen generator, adopting boiling point is that 40～65 ℃ of ammonium bicarbonates are the cracking hydrogen production raw material, and using the material carbon ammonium is the prescription of 1 to 1～1.2 weight ratios than water, at nickeliferous 40～60%, platinum palladium 0.05～0.2% and K, Al
2O
3Under the catalyst action, reach 300～760 ℃, pressure at the hydrogen generator bed temperature and reach and carry out the gasification cracking reaction under 0.02～4 MPa condition, produce hydrogen-rich gas.
6, according to the described technology of claim 5, it is characterized in that adopting volatile salt or bicarbonate of ammonia is 1 to 1～1.2 weight ratio than water.
7, for realizing the custom-designed hydrogen generator of cracking hydrogen production technology (1) of claim 1 or 3 or 5, it is characterized in that described hydrogen generator directly is serially connected on the gas exhaust duct of engine (50) (56), be combined into one with the exhaust snubber of engine, its internal structure connects into the U-shaped structure by the hot cell of gasifying (10) and reaction chamber (19) through communicating pipe (2), on its inwall both sides, hot cell of gasifying (10) gas channel, a few row's pectination ultrasonic vibration reeds are set, the feeder system of hydrogen generator is by alcohol (water) case (49), valve (43a, b), pump (36,46), pipeline (28) is formed, carry the hydrogen-rich gas system by pipeline (31), air tank (41), valve (44), fuel mixer (48) is formed, wherein fuel mixer (48) is the ultrasonic device structure of vortex, engine exhaust passage is to follow pipeline (56), through bypassing exhaust valve (42), enter hydrogen generator then, be discharged into atmosphere by pipeline (37), when temperature reaches set(ting)value, by thermopair temperature controller (58) instruction electricity alcohol (water) pump startup, to the hydrogen generator feed, when temperature surpasses preset value, make bypassing exhaust by thermopair temperature controller (58) electromagnetic valve of instruction, follow pipeline (7) and be discharged into atmosphere.
8, hydrogen generator according to claim 7, the vibrating reed material in the hot cell (10) that it is characterized in that gasifying be with stainless steel or steel nickel chrome, thickness 0.2mm～2.4mm, and vibrational frequency is the 8000-24000 kilocycle.
9, hydrogen generator according to claim 7 is characterized in that fuel mixer (48) is the ultrasonic device structure of vortex, and the air outlet is to locate in volute inwall lower edge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100965A CN1043027C (en) | 1996-01-18 | 1996-01-18 | Cracking process for producing hydrogen and sepecial equipment for producing hydrogen |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100965A CN1043027C (en) | 1996-01-18 | 1996-01-18 | Cracking process for producing hydrogen and sepecial equipment for producing hydrogen |
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| Publication Number | Publication Date |
|---|---|
| CN1134912A CN1134912A (en) | 1996-11-06 |
| CN1043027C true CN1043027C (en) | 1999-04-21 |
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| CN96100965A Expired - Fee Related CN1043027C (en) | 1996-01-18 | 1996-01-18 | Cracking process for producing hydrogen and sepecial equipment for producing hydrogen |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039814A (en) * | 2009-10-26 | 2011-05-04 | 韩林生 | Hydrogen vehicle capable of producing hydrogen by alcohol cracking |
| CN102358617B (en) * | 2011-06-29 | 2013-07-10 | 西安交通大学 | Methanol hydrogen production apparatus, and method for preparing hydrogen by using the same |
| CN102431434B (en) * | 2011-11-22 | 2016-06-22 | 昆明新能源发展有限公司 | Hydrogen cell mixed power automobile |
| CN105600749A (en) * | 2015-10-16 | 2016-05-25 | 陈昌洪 | Method for synthesizing hydrogen fuel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2743171A (en) * | 1950-08-23 | 1956-04-24 | United Gas Improvement Co | Method for making gas rich in hydrogen |
| GB2136788A (en) * | 1983-03-25 | 1984-09-26 | Metallgesellschaft Ag | Process for heating hydrogen under pressure |
| DE3528858A1 (en) * | 1985-08-12 | 1987-02-19 | Caloric Ges Apparatebau | Process and plant for producing synthesis gas by cracking of hydrocarbons |
| CN1068589A (en) * | 1992-07-11 | 1993-02-03 | 苏培 | Fuel-oil cracked gas burning process and equipment |
-
1996
- 1996-01-18 CN CN96100965A patent/CN1043027C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2743171A (en) * | 1950-08-23 | 1956-04-24 | United Gas Improvement Co | Method for making gas rich in hydrogen |
| GB2136788A (en) * | 1983-03-25 | 1984-09-26 | Metallgesellschaft Ag | Process for heating hydrogen under pressure |
| DE3528858A1 (en) * | 1985-08-12 | 1987-02-19 | Caloric Ges Apparatebau | Process and plant for producing synthesis gas by cracking of hydrocarbons |
| CN1068589A (en) * | 1992-07-11 | 1993-02-03 | 苏培 | Fuel-oil cracked gas burning process and equipment |
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|---|---|
| CN1134912A (en) | 1996-11-06 |
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