CN1900040A - Near azeotropic ethanol dewatering process - Google Patents
Near azeotropic ethanol dewatering process Download PDFInfo
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- CN1900040A CN1900040A CN 200610043134 CN200610043134A CN1900040A CN 1900040 A CN1900040 A CN 1900040A CN 200610043134 CN200610043134 CN 200610043134 CN 200610043134 A CN200610043134 A CN 200610043134A CN 1900040 A CN1900040 A CN 1900040A
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Abstract
The near azeotropic ethanol mixture dewatering process includes the following steps: filling the reaction section of reacting rectification tower with cylindrical solid acid catalyst stuffing and feeding near azeotropic ethanol-water mixture; introducing N2 into the tower for pressurizing, adding C4 fraction, heating and regulating pressure for total reflux operation; setting reflux ratio and adding ethanol-water mixture and C4 fraction based on the set material ratio; condensing the tower top product, returning partial tower top product to the tower while collecting the rest in the tower top storage tank; and collecting the tower bottom product through the bottom condenser with the bottom storage tank as the anhydrous alcohol-ether mixture fuel.
Description
Technical field
The present invention relates to a kind of ethanol dewatering method, particularly a kind of near azeotropic ethanol dewatering process.
Background technology
Ethanol petrol (claiming gasohol again) is to add a kind of novel environmental friendliness propellant combination that a certain proportion of denatured fuel ethanol forms in gasoline.Because of ethanol itself has higher octane value, harmonicity and contain the oxygen and aiding combustion characteristic preferably, therefore, after automobile uses ethanol petrol, oil consumption and dynamic performance change little, but the carbon monoxide average discharge reduces more than 60%, and the quantity discharged of hydrocarbon polymer descends more than 10%, simultaneously, ethanol can make with the means of biological fermentation, be a kind of renewable energy source, therefore, promote the use of ethanol petrol, can reduce dependence greatly to petroleum resources, help to set up independently economy of energy system, reduce mobile pollutant emission, improve environmental quality and stimulate agricultural development etc.
Present many countries aspect the development and popularization use of alcohol fuel, have carried out a series of fruitful work, and the ability of now producing alcohol fuel as Brazil has reached 1,000 ten thousand tons/year, and existing 33% uses alcohol fuel in the vehicle fuel.The U.S. has just formulated " ethanol plan " as far back as the middle of last century, has had 41 states promoting the use of vehicle-use alcohol gasoline at present, and the consumption of ethanol petrol has surpassed 20% of whole gasoline consumptions.Thailand is the country of first introduction alcohol fuel technology of Asia, has now set up the self-centered economy of energy system of producing, selling and uying based on novel energy.The industrialization development of China recent years alcohol fuel is also very rapid, produces alcohol fuel and has classified national demonstration project major project as, and the fuel ethanol production project of domestic a collection of ten tons is constructed and put into operation.
The preparation process of the ethanol petrol of domestic and foreign current is earlier the biological fermentation ethanol dewatering to be made volume fraction at the high concentration fuel ethanol more than 99%, will mix according to a certain percentage with regular price gasoline after this high concentration fuel ethanol denaturing treatment again.The key of this process is the purification technique that dewaters of bio-ethanol.Because there is constant boiling point in ethanol-water system under the normal pressure, conventional rectification can only obtain the ethanol of azeotropic concentration, and the ethanol volume fraction only is about 95%, can not satisfy the content requirement of vehicle fuel to water.Removing of water in the azeotropic concentration ethanol must be adopted special separation means.
Be used at present the special separation technology utilization of ethanol dehydration more azeotropic distillation, extracting rectifying, molecular sieve adsorption etc. are arranged.As Duan Zhanting etc. " a kind of one-step composite extraction and rectification is produced the method for dehydrated alcohol " (Chinese patent application 01118357.8) proposed, the composite extractant that this process using is made up of solvent, Reaction Separation agent and salting-out agent will contain ethanol and be 70～80% aqueous ethanolic solutions and purify to purity greater than 99.8% dehydrated alcohol product in extractive distillation column.Though above-mentioned technology can obtain the ethanol of higher concentration, weak point is that energy consumption is bigger, and flow process is longer, and a spot of nonvariant boiling reagent or extraction agent are sneaked into to subsequent separation process and brought sizable extras and energy investment, and product performance are affected.Gu Zhaolin etc. have proposed a kind of " alcohol fuel heat pump sequence of constant boiling and rectification technology and device " (Chinese patent application 02145503.1), and sequence of constant boiling and rectification and two kinds of proven technique of heat pump techniques are combined, and develop heat pump sequence of constant boiling and rectification new process of production.Though the more traditional sequence of constant boiling and rectification technology of this technology has energy-conservation effect, but still need the ethanol dehydration tower, the entrainment agent recovery tower, more equipment such as alcohol distillation column, the facility investment expense is still higher.Zhang Minhua etc. have proposed a kind of " production of alcohol fuel " (Chinese patent application 200410094085.0) that adopts molecular sieve adsorbing and dewatering, it is on the high side that the sieve method dehydration exists sorbent material, the finished product recovery rate is on the low side and lost efficacy after the defective that can only handle as waste residue, and the regeneration energy consumption of molecular sieve is also bigger.
Kochar etc. have proposed an ethanol dewatering process (US 4334890).In this technology, aqueous ethanol and C-4-fraction react on acid catalyst, generate the propellant combination of alcohol, ether.In the technical process that they design at this thinking, comprise an extraction tower, two reactors and two rectifying tower.This technology has certain innovation, independently carries out but react with lock out operation, and technical process is too complicated, and equipment energy consumption, production cost are still higher.
To sum up, the production of fuel ethanol cost is to be related to the important indicator that whole vehicle-use alcohol gasoline is promoted complexity.Generally speaking, the grain cost of China makes that than higher alcohol after the fermentation is on the high side, adds the rectifying production cost, and the price of alcohol fuel is compared with regular gasoline, does not have tangible competitive power at present.Therefore, developing new pure water separation technology, to reduce the energy consumption and the investment of producing alcohol fuel, reduce production costs, and further enhance product performance, is present mass-producing ethanol petrol key issue to be solved production phase.
Summary of the invention
The purpose of this invention is to provide that a kind of to have a technical process simple and easy, equipment energy consumption and production cost are low, the near azeotropic ethanol dewatering process that product yield is high, this technology utilization reaction and separation coupling technology, when carrying out, chemical reaction imports lock out operation, the water that makes conventional separation method be difficult to remove generates other materials by reactive distillation, and direct then and gasoline blending is used.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of near azeotropic ethanol dewatering process comprises the steps:
A. at first at the cylindric solid acid catalyst filler of the conversion zone filling of reaction fractionating tower, in the tower still, add the near azeotropic ethanol-water mixture feed liquid of suitable tower still capacity 1/2;
B. then by feeding N to cat head
2Full tower is boosted, add suitable tower still capacity 1/3 C-4-fraction from the conversion zone bottom, giving the heating of tower still again and progressively adjusting pressure is 1.0～2.0MPa, carries out total reflux operation;
C. after total reflux operation half an hour, set reflux ratio 5～10, by ethanol-water mixture and the charging of C-4-fraction feeding rate set, ethanol-water mixture is squeezed in the tower from the conversion zone upper end after preheating by metering piston pump, and C-4-fraction is squeezed in the tower from the conversion zone lower end after preheating by metering piston pump;
D. overhead product passes back into tower by a reflux ratio part of setting after condenser condenses, and a part enters the cat head storage tank and collects; Bottom product enters the still liquid storage tank by tower still discharge port by still liquid cooling condenser and collects;
E. after the operation of reaction fractionating tower reaches steady state, carry out the operate continuously of step c again, the still liquid storage tank is collected is the anhydrous alcohol ether propellant combination of gained.
In the such scheme, the preparation method of the cylindrical catalyst filler of conversion zone filling is: the rectangular block that earlier 60 order stainless (steel) wires is cut into desired size, be rolled into cylindric again, the cylinder of filling solid acid catalyst bulk granular inside, and sealing then both ends of the surface required cylinder shape catalyst filler; Described catalyzer is S-54 or NKC-9 Zeo-karb; The concentration of described near azeotropic ethanol-water mixture is for containing ethanol 85～90wt%.Adopting concentration is the purpose of near azeotropic ethanol-water mixture of 85～90wt%, be to reduce the energy consumption of conventional rectification process on the one hand, because correlative study shows, in with conventional rectification purification alcoholic acid process, when alcohol concn further raising along with alcohol concn during in 85% left and right sides, the energy consumption of rectifying increases sharply; On the other hand, the ethanol price of the nearly azeotropic concentration of 85～90wt% is lower than the straight alcohol price, can further reduce raw materials cost.
Temperature of reaction of the present invention is that reactive distillation Tata temperature in the kettle is 130～185 ℃, and tower head (condenser) temperature is 90～105 ℃, and the tower head and the tower still temperature difference are bigger, show that separating effect is apparent in view; The pressure that is adopted is 1.0～2.0Mpa, and this pressure range can make and be reflected at the liquid phase generation; The charging flow velocity of described ethanol-water mixture and C-4-fraction is respectively 45～50ml/h and 188～263ml/h.
The mechanism of technical solution of the present invention is, with solid acid such as homemade Zeo-karb such as S-54, NKC-9 etc. is catalyzer, pass through reactive distillation process, making concentration is that isobutene reaction in the C-4-fraction of water near azeotropic ethanol-water mixture of 85～90wt% and refinery gas generates the trimethyl carbinol, and part ethanol etherificate generates Ethyl Tertisry Butyl Ether.And do not participate in the C-4-fraction that reacts, will from system, remove to use it for anything else by refinery distillation.
The invention has the beneficial effects as follows:
(1) the present invention carries out when having realized hydration, etherificate complex reaction and rectifying separation in a device, the water that should remove in the middle of the ethanol, obtain the trimethyl carbinol by reaction, the mixture that Ethyl Tertisry Butyl Ether and part ethanol constitute has been realized atomic economy reaction.The octane value of product is higher than methyl tertiary butyl ether, and vapour pressure is lower than methyl tertiary butyl ether, is a kind of good vehicle fuel, can directly mix use with gasoline.
(2) react with the elder generation of external report; the ethanol dewatering process of rectifying separation is compared again; the present invention has adopted the reactive distillation coupling technique; correlated process concentrates in the reaction fractionating tower carries out; made full use of reaction heat; thereby simplified flow process, and significantly reduced energy consumption, facility investment and production cost, can realize ethanol petrol large-scale production efficiently.
(3) use of C-4-fraction among the present invention is for new approach has been opened up in the utilization of refinery gas.
Description of drawings
Fig. 1 is the employed plant system drawing of method of the present invention.
Among the figure, 1 is the ethanol-water mixture storage tank; 2 is the C-4-fraction steel cylinder; 3 is the cat head storage tank; 4 is condensate draining; 5 is the still liquid storage tank; 6 is reaction fractionating tower, and wherein A is the tower still, and B is a stripping section, and C is a conversion zone, and D is a rectifying section, and E is a reflux section, and F is a condenser; 7 are the backflow controller; 8 is still liquid cooling condenser; 9 is N
2Steel cylinder; 10 is housing; 11 is computer.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
As shown in Figure 1, reaction fractionating tower 6 of the present invention is by tower still A, stripping section B, conversion zone C, rectifying section D, reflux section E, condenser F constitutes, the cylindrical catalytic filler that conversion zone C filling is made by solid acid catalyst, rectifying section D and stripping section B filling stainless (steel) wire θ ring filler are of a size of 2 * 2mm.The internal diameter of reaction fractionating tower 6 is 25mm, stripping section B, conversion zone C and each 500mm of rectifying section D height.The capacity of tower still A is 1500ml, adopts Electric heating, and maximum heating power is 25kW, uses thermocouple and automatic instrument to detect the control Heating temperature.Other each section also adopts the thermocouple detected temperatures in the tower, adopts Electric heating and automatic instrument controlled temperature, can reduce the tower body heat lost by radiation.Condenser F is a vertical type, and condensation area is 0.16m
2, cooling medium is a water.
The self-control cylindrical catalyst dumped packing of conversion zone C filling, be of a size of 5 * 5mm, its preparation method is as follows, earlier 60 order stainless (steel) wires are cut into the rectangular block of desired size, be rolled into cylindric again, load S-54 strongly acidic cation-exchange granules of catalyst then inside, and sealing cylinder both ends of the surface required cylinder shape catalyst filler, catalyzer also can adopt homemade Zeo-karbs such as NKC-9.
The concentration of the reactant near azeotropic ethanol-water mixture that is adopted is for containing ethanol 85～90wt%, preferred 90wt%; The C-4-fraction that is adopted is the C-4-fraction of raw material refinery gas, and quality group becomes iso-butylene 15.2%, n-butene 15.0%, and normal butane 36.19%, Trimethylmethane 12.6%, dibutene are 17.47%, other ingredients constitute 3.54%; Its reactive behavior thing is that isobutyl is rare;
Below by the specific embodiment of the invention and comparative example, further specify beneficial effect of the present invention.
Embodiment 1
A. at first at the cylindric solid acid S-54 of the conversion zone C of reaction fractionating tower 6 filling resin catalyst filler, in tower still A, add the ethanol-water mixture feed liquid of 700ml 85wt%;
B. cat head feeds N then
2Make full tower pressurization, add the 500ml C-4-fraction from the conversion zone bottom, giving 6 heating of tower still again and progressively adjusting pressure is 1.5MPa, carries out total reflux operation;
C. after total reflux operation extremely full column foot half an hour was originally stablized, setting reflux ratio was 5, begins charging.During charging, ethanol-water mixture is added in the reaction fractionating tower 6 from conversion zone C upper end after preheating by the metering piston pump of storage tank 1, the charging flow velocity is 45.0ml/h, C-4-fraction is added in the reaction fractionating tower 6 from conversion zone C lower end after preheating by the metering piston pump of steel cylinder 2, and the charging flow velocity is 188.0ml/h;
D. overhead product passes back into tower by a reflux ratio part of setting after condenser F condensation, and a part enters cat head storage tank 3 and collects; Bottom product enters still liquid storage tank 5 by tower still A discharge port by still liquid cooling condenser 8 and collects;
E. after the operation of tower reached steady state, temperature was 133 ℃ in the tower still A, and the tower head temperature is 90 ℃, carries out operate continuously again, and still liquid storage tank 5 is collected is prepared high-performance alcohol ether propellant combination.
Adopt GC122 type gas chromatograph analytic sample to form.Chromatogram column length 3m, in fill the Gaschropack-54 carrier, the processing of chromatographic data is adopted the relative correction normalization method to carry out peak area quantification and is calculated.Analysis condition is: 160 ℃ of post oven temperature, degree, temperature of vaporization chamber are 180 ℃, and the TCD temperature is 180 ℃, TCD electric current 100mA, carrier gas H
2, carrier gas flux is 60mlmin
-1
Analyze the alcohol ether propellant combination that embodiment 1 prepares with above-mentioned gas chromatograph, the quality group of product becomes water 1.72%, ethanol 1.89%, the trimethyl carbinol 11.78%, Ethyl Tertisry Butyl Ether 84.61%, the transformation efficiency of water are 71.05%, and the products obtained therefrom blending octane rating is 109.15.
A. at first at the cylindric solid acid S-54 of the conversion zone C of reaction fractionating tower 6 filling resin catalyst filler, in tower still A, add the ethanol-water mixture feed liquid of 700ml 90wt%;
B. cat head feeds N then
2Make full tower pressurization, and add the 500ml C-4-fraction, giving tower still A heating again and progressively adjusting pressure is 2.0MPa, carries out total reflux operation;
C. after total reflux operation extremely full column foot half an hour was originally stablized, setting reflux ratio was 10, begins charging.During charging, ethanol-water mixture is added in the reaction fractionating tower 7 from conversion zone C upper end after preheating by the metering piston pump of storage tank 1, the charging flow velocity is 47.74ml/h, C-4-fraction is added in the reaction fractionating tower 6 from conversion zone C lower end after preheating by the metering piston pump of steel cylinder 2, and the charging flow velocity is 263.0ml/h;
D. with the steps d of embodiment 1;
E. after the operation of tower reached steady state, temperature was 181 ℃ in the tower still A, and the tower head temperature is 104 ℃, carries out operate continuously again, and still liquid storage tank 5 is collected is prepared high-performance alcohol ether propellant combination.
Use the gas chromatograph analysis, the quality group of the finished product becomes water 0.4%, ethanol 0.7%, the trimethyl carbinol 23.2%, Ethyl Tertisry Butyl Ether 75.7%.The transformation efficiency of water is 92.4%.The products obtained therefrom blending octane rating is 108.49.
A. with the step a of embodiment 2;
B. with the step b of embodiment 1;
C. after total reflux operation extremely full column foot half an hour was originally stablized, setting reflux ratio was 5, begins charging.During charging, ethanol-water mixture is added in the reaction fractionating tower 6 from conversion zone C upper end after preheating by the metering piston pump of storage tank 1, the charging flow velocity is 47.74ml/h, C-4-fraction is added in the reaction fractionating tower 7 from conversion zone C lower end after preheating by the metering piston pump of steel cylinder 2, and the charging flow velocity is 263.0ml/h.
D. with the steps d of embodiment 1;
E. after the operation of tower reached steady state, temperature was 130 ℃ in the tower still A, and the tower head temperature is 90 ℃, carries out operate continuously again, and still liquid storage tank 5 is collected is prepared high-performance alcohol ether propellant combination.
Use the gas chromatograph analysis, the quality group of the finished product becomes water 0.4%, ethanol 3.1%, the trimethyl carbinol 16.7%, Ethyl Tertisry Butyl Ether 79.8%.The transformation efficiency of water is 91.2%.The products obtained therefrom blending octane rating is 109.68.
Embodiment 4
A. with the step a of embodiment 1;
B. cat head feeds N then
2Make full tower pressurization, give tower still A pressurization and add the 500ml C-4-fraction, giving tower still A heating again and progressively adjusting pressure is 1.7MPa, carries out total reflux operation;
C. with the step c of embodiment 3;
D. with the steps d of embodiment 1;
E. after the operation of tower reached steady state, temperature was 146 ℃ in the tower still A, and the tower head temperature is 96 ℃, carries out operate continuously again, and still liquid storage tank 5 is collected is prepared high-performance alcohol ether propellant combination.
Use the gas chromatograph analysis, the quality group of the finished product becomes water 0.4%, ethanol 4.7%, the trimethyl carbinol 26.7%, Ethyl Tertisry Butyl Ether 68.2%.The transformation efficiency of water is 77.7%.The products obtained therefrom blending octane rating is 108.58.
A. at first at the cylindric solid acid NKC-9 of the conversion zone C of reaction fractionating tower 6 filling resin catalyst filler, in tower still A, add the ethanol-water mixture feed liquid of 700ml 90wt%;
B. cat head feeds N then
2Make full tower pressurization, give tower still A pressurization and add the 500ml C-4-fraction, giving tower still A heating again and progressively adjusting pressure is 2.0MPa, carries out total reflux operation;
C. after total reflux operation extremely full column foot half an hour was originally stablized, setting reflux ratio was 10, begins charging.During charging, the 85wt% ethanol-water mixture is added in the reaction fractionating tower 7 from conversion zone C upper end after preheating by the metering piston pump of storage tank 1, the charging flow velocity is 50.0ml/h, C-4-fraction is added in the reaction fractionating tower 6 from conversion zone C lower end after preheating by the metering piston pump of steel cylinder 2, and the charging flow velocity is 240.0ml/h.
D. with the steps d of embodiment 1;
E. after the operation of tower reached steady state, temperature were 171 ℃ in the tower still 6, and the tower head temperature is 104 ℃, carries out operate continuously again, and still liquid storage tank 5 is collected is prepared high-performance alcohol ether propellant combination.
Use the gas chromatograph analysis, the quality group of the finished product becomes water 0.4%, ethanol 5.5%, the trimethyl carbinol 35%, Ethyl Tertisry Butyl Ether 59.1%.The transformation efficiency of water is 89.0%.The products obtained therefrom blending octane rating is 107.59.
Comparative example 1
The ethanol of 1.76mol, water and 20.35g 40～60 purpose S-54 resins of 0.5mol are joined in the high pressure stainless steel cauldron, use nitrogen purging with air in the displacement still earlier, and be pressurized to about 1.3MPa, again toward the interior iso-butylene that adds 3.5mol of reactor.Make reaction solution heat to 60 ℃ rapidly, regulate pressure to 2.0MPa.Starting agitator, to make rotating speed be 600rpm.When 6h was carried out in reaction, reaction reached balance, analyzes with gas chromatograph, the quality group of the finished product becomes water 2.26%, iso-butylene 5.49%, ethanol 13.84%, the trimethyl carbinol 25.51%, Ethyl Tertisry Butyl Ether 52.90%, products obtained therefrom blending octane rating are 105.79.
Comparative example 2
The ethanol of 3.52mol, water and 30g 40～60 purpose NKC-9 resins of 1mol are joined in the high pressure stainless steel cauldron, use nitrogen purging with air in the displacement still earlier, and be pressurized to about 1.3MPa, again toward the interior iso-butylene that adds 3.0mol of reactor.Make reaction solution heat to 90 ℃ rapidly, regulate pressure to 2.0MPa.Starting agitator, to make rotating speed be 600rpm.When 6h was carried out in reaction, reaction reached balance, uses the gas chromatograph analysis, and the quality group of the finished product becomes water 3.03%, iso-butylene 2.0%, and ethanol 47.5%, the trimethyl carbinol 11.2%, Ethyl Tertisry Butyl Ether 36.00%, products obtained therefrom blending octane rating are 106.13.
More than adopt two comparative examples of simple operation to show: though also finished the fractional conversion of water, the ethyl tert-butyl ether content is lower, and the octane value of gained mixture is lower than the octane value of the present invention reactive distillation operation gained alcohol ether propellant combination.
Claims (6)
1. a near azeotropic ethanol dewatering process is characterized in that, comprises the steps:
A. at first at the cylindric solid acid catalyst filler of the conversion zone C of reaction fractionating tower (6) filling, in tower still A, add the near azeotropic ethanol-water mixture feed liquid of suitable tower still capacity 1/2;
B. feed N2 gas from cat head full tower is boosted, add the C-4-fraction of suitable tower still capacity 1/3 from conversion zone C bottom, giving tower still A heating again and progressively adjusting pressure is 1.0～2.0MPa, carries out total reflux operation;
C. after total reflux operation half an hour, set reflux ratio 5～10, add ethanol-water mixture and C-4-fraction by the feeding rate of setting, ethanol-water mixture is squeezed in the tower from conversion zone C upper end after preheating by metering piston pump, and C-4-fraction is squeezed in the tower from conversion zone C lower end after preheating by metering piston pump;
D. overhead product passes back into tower by a reflux ratio part of setting after condenser F condensation, and a part enters cat head storage tank (3) and collects; Bottom product enters still liquid storage tank (5) by tower still A discharge port by still liquid cooling condenser (8) and collects;
E. after the operation of reaction fractionating tower (6) reaches steady state, carry out the operate continuously of step c again, still liquid storage tank (5) is collected is anhydrous alcohol ether propellant combination.
2. near azeotropic ethanol dewatering process according to claim 1, it is characterized in that, among the step a, the preparation method of the cylindrical catalyst filler of described conversion zone C filling is: the rectangular block that earlier 60 order stainless (steel) wires is cut into desired size, be rolled into cylindric again, the cylinder of filling solid acid catalyst bulk granular inside, and sealing then both ends of the surface required cylinder shape catalyst filler.
3. alcohol ether propellant combination preparation technology according to claim 1 and 2 is characterized in that, described solid acid catalyst is S-54 or NKC-9 Zeo-karb.
4. near azeotropic ethanol dewatering process according to claim 1 is characterized in that, among the step a, the concentration of described near azeotropic ethanol-water mixture is for containing ethanol 85～90wt%.
5. near azeotropic ethanol dewatering process according to claim 1 is characterized in that, among the step c, described ethanol-water mixture and C-4-fraction feeding rate are respectively 45～50ml/h and 188～263ml/h.
6. near azeotropic ethanol dewatering process according to claim 1 is characterized in that, among the step e, after the operation of described reaction fractionating tower (6) reached steady state, temperature was 130～185 ℃ in the tower still A, and the tower head temperature is 90～105 ℃.
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| CNB2006100431347A CN100386299C (en) | 2006-07-10 | 2006-07-10 | Near azeotropic ethanol dewatering process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471385A (en) * | 2009-07-28 | 2012-05-23 | Cp凯可股份公司 | Dewatering biomass material comprising polysaccharide, method for extracting polysaccharide from biomass material, and dewatered biomass material |
| CN109913505A (en) * | 2019-04-30 | 2019-06-21 | 广州市广环环保科技有限公司 | A method of alcohol fuel is produced using kitchen garbage |
| CN110668920A (en) * | 2019-09-20 | 2020-01-10 | 华中科技大学 | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334890A (en) * | 1981-02-03 | 1982-06-15 | The Halcon Sd Group, Inc. | Process for gasoline blending stocks |
-
2006
- 2006-07-10 CN CNB2006100431347A patent/CN100386299C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471385A (en) * | 2009-07-28 | 2012-05-23 | Cp凯可股份公司 | Dewatering biomass material comprising polysaccharide, method for extracting polysaccharide from biomass material, and dewatered biomass material |
| CN109913505A (en) * | 2019-04-30 | 2019-06-21 | 广州市广环环保科技有限公司 | A method of alcohol fuel is produced using kitchen garbage |
| CN110668920A (en) * | 2019-09-20 | 2020-01-10 | 华中科技大学 | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method |
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