CN103864573A - Method for preparing chemical products by direct hydrothermal hydrogenation of microalgae - Google Patents
Method for preparing chemical products by direct hydrothermal hydrogenation of microalgae Download PDFInfo
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- CN103864573A CN103864573A CN201410092469.2A CN201410092469A CN103864573A CN 103864573 A CN103864573 A CN 103864573A CN 201410092469 A CN201410092469 A CN 201410092469A CN 103864573 A CN103864573 A CN 103864573A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention discloses a method for preparing chemical products by direct hydrothermal hydrogenation of microalgae. The method comprises the following steps: adding the microalgae and water into a reactor, and performing hydrogenation hydrogenolysis reaction in the presence of a catalyst with hydrogenation hydrogenolysis activity for 10-360 minutes to obtain the chemical products. The method can be used for preparing the chemical products with high added values such as dihydric alcohol and acetone alcohol, and CO2 can be subjected to high-efficiency biological fixation and chemical conversion as the microalgae as new environment-friendly renewable biomass energy resources are utilized.
Description
Technical field
The present invention relates to a kind of method of preparing chemical, particularly relate to a kind of by micro-algae Direct Hydrothermal Hydrogenation the method for chemical.
Background technology
Dibasic alcohol is very important polyester high polymer monomer, can be used for producing unsaturated polyester resin, urethane, fuel dope, tensio-active agent, emulsifying agent, antifreeze solution of motorcycle etc., its most important purposes is to produce unsaturated polyester (UPR), within 2010, China's UPR turnout is 1,700,000 tons, 500,000 tons of consumption dibasic alcohol, market outlook are wide.Greatly and rely on import, petroleum-based production line is difficult to continue China's dibasic alcohol demand simultaneously more; Current domestic relevant enterprise adopts W-Gum be raw material by enzymic hydrolysis refine sugar, the technique of sugared hydrogenation hydrogenolysis prepares dibasic alcohol, but there is the problem of " strive grain, strive ground with grain with people " taking grain as raw material production chemical, development has been subject to serious actual restriction; Along with the exhaustion day by day of the fossil energy such as crude oil, coal, it is imperative that the bio-based dibasic alcohol that is raw material based on reproducible non-grain biomass is produced variation route.
The Wang Yong of Shandong Xiwang Sugar Co., Ltd etc. discloses a kind of method (CN1915947A that utilizes vegetable fibre to prepare polyvalent alcohol through acidic hydrolysis, hydrogenation hydrogenolysis, 2007), the method adopts acid hydrolysis treatment process, and equipment is had to certain corrosion, and it is more difficult that follow-up acid waste water is processed; The people such as Xu Jie have proposed a kind of method (CN101704710A, 2010) of carrying out catalytic conversion on corn cobs dibasic alcohol, and corn cob is prepared the polyvalent alcohol product of high yield through processes such as acid-catalyzed hydrolysis, shortenings; The human hairs such as Chen Hongzhang understand that the liquefaction of a kind of straw prepares the method (CN101172932A, 2008) of polyvalent alcohol, and straw adds polyvalent alcohol and sulfuric acid to react under certain condition to obtain biopolyol after steam explosion; Above-mentioned technique adopts liquid acid to the biomass pre-treatment that is hydrolyzed more, thereby to the higher installation cost that increased of equipment requirements, brought certain environmental problem, the introducing of acid system makes a large amount of impurity strippings in biomass, brings difficulty to later separation and purification simultaneously.The superfine people of bang has proposed a kind of method of Mierocrystalline cellulose production sorbyl alcohol and N.F,USP MANNITOL, utilize the original position protonic acid hydrocellulose of water self under hydrothermal condition, hydrolysis intermediate product is carried out to coupling hydro to prepare sorbyl alcohol and N.F,USP MANNITOL simultaneously, in reaction process without soda acid, but the selectivity of glycol is very low below 15% (CN101058531A, 2007); The researchist of the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences utilizes non-precious metal catalyst wolfram varbide to be applied to cellulosic catalyzed conversion, at 245 DEG C, react 30min taking Activated Carbon Supported wolfram varbide as catalyzer, the yield of ethylene glycol is 29%, under the promotion of a small amount of nickel, the yield of ethylene glycol is up to 61%(CN101648140A, and 2010).The pure Mierocrystalline cellulose of the many employings of these methods is raw material, and required Mierocrystalline cellulose majority extracts from lignocellulose, and cost is higher and expensive.The people such as Mu Xingdong have proposed raw materials pretreatment, Enzymatic hydrolysis and the shortening hydrogenolysis technology technique that is coupled and have prepared glycol products, wherein the yield of propylene glycol can reach 29.8%, but this process raw material needs acid-base pretreatment, enzymatic saccharification required time is long and cost is high, bring certain inconvenience (CN102286548A, 2011) to actually operating.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of by micro-algae Direct Hydrothermal Hydrogenation the method for chemical.The present invention is by gentle controlled hydro-thermal reaction system, can prepare the chemical of the high added value such as dibasic alcohol and hydroxyacetone, and owing to having utilized this eco-friendly renewable biomass new forms of energy of micro-algae, can realize the high-performance bio of CO2 and fix and chemical conversion.
For solving the problems of the technologies described above, micro-algae Direct Hydrothermal Hydrogenation of the present invention, for the method for chemical, comprises step:
In reactor, add algae and water in a subtle way, and have under the catalyst action of hydrogenation hydrogenolysis activity, carry out hydrogenation hydrogenolysis 10～360min in 150～300 DEG C, obtain chemical.
Wherein, described reactor is preferably intermittent type or flow reactor.
Described micro-algae comprises: the micro-algae of common fresh water or seawater, as comprise: one or more in grid algae, chlorella, salt algae, chlamydomonas, Chlorococcum etc.Wherein, the carbohydrate content of micro-algae is 40～65wt%(mass percent), nitrogen content is 0～0.5wt%(mass percent), sulphur content is 0～0.5wt%(mass percent).
The solid-to-liquid ratio of micro-algae and water is preferably 1g:100mL～50g:100mL.
Described catalyzer can be the conventional catalyzer with hydrogenation hydrogenolysis activity, comprising: a kind of in loaded catalyst and unsupported catalyst or their combination.Wherein, preferably, the active ingredient of this catalyzer comprises: group VIII metal element and subgroup metallic element; Wherein, group VIII metal element comprises: Ni, Ru or Pt; Subgroup metallic element comprises: Cu, Zn, Cr, Mo or W.The carrier of loaded catalyst comprises: gac (AC), diatomite, aluminum oxide or zeolite molecular sieve.
In described hydrogenation hydrogenolysis, the original pressure of hydrogen is 1.0～8.0MPa.
Described chemical comprises: dibasic alcohol and hydroxyacetone etc. that carbonatoms is 2～6.
In the method for micro-algae Direct Hydrothermal Hydrogenation of the present invention for chemical, described catalyzer through solid-liquid separation, dry after, can use by cyclic regeneration.
The present invention, compared with existing dibasic alcohol technology of preparing, has following advantage:
1) micro-algae is as a kind of waterplant, have that short, the solid carbon efficiencies of growth cycle is high, fecundity by force, easily cultivate, be easy to possession, tolerate the characteristic of the aspects such as extreme environment, effectively fixed co2 of micro-algae propagation process itself, can make full use of pond, coastal marine site, beach, wetland etc. carries out artificial propagation and is used, micro-algae raw material sources are extensive, not there is not the problem of " striving grain with people ", meet the inherent requirement of Sustainable development; In micro-algae, contain abundant carbohydrate generally in 50% left and right, cultivate can make it to reach by enhancing orientation and more than 60% become the sugared algae of being rich in carbohydrate, sugar algae is rich in carbohydrate and low nitrogen sulphur content, and it is the high quality raw material for dibasic alcohol as hydro-thermal Hydrogenation directly; Micro-algae hydro-thermal Hydrogenation can process for glycol products the algae pollutant that causes body eutrophication effectively, realizes its recycling.
2) to propose to be first rich in micro-algae of carbohydrate be that raw material directly carries out hydro-thermal hydrogenation hydrogenolysis and prepares glycol products in the present invention, after micro-algae is concentrated, water ratio is all more than 90%, micro-algae Direct Hydrothermal Hydrogenation for dibasic alcohol process Raw without dry, micro-algae just can carry out Direct Hydrothermal hydrogenation hydrogenolysis after simple concentrated collection, realize micro-algae hydrolysis, the one step realization of hydro-thermal hydrogenation catalyst hydrogenolysis, be somebody's turn to do " one kettle way " hydro-thermal hydrogenation hydrogenolysis mild condition, transformation efficiency is high, good to the selectivity of target product dibasic alcohol.
3) product of the present invention is mainly that carbonatoms is 2～6 dibasic alcohol and important intermediate hydroxyacetone, dibasic alcohol is mainly with propylene glycol (1,2-propylene glycol) be main, can separate rear independent use, also can separate to be directly used in without the degree of depth and produce unsaturated polyester resin, urethane, fuel dope, tensio-active agent, emulsifying agent, antifreeze solution of motorcycle etc., there is many potential uses; Hydroxyacetone is as important organic synthesis intermediate, of many uses.
4) the present invention is that a kind of novel, green and power-economizing method are prepared chemical, have broad application prospects, the technique that adopts is simple, less investment, energy consumption is low, output is high, green non-pollution, technological process is easily controlled, can be intermittently and continuous operation, catalyzer recoverable, is applicable to large-scale industrial production.Brief description of the drawings
Below in conjunction with accompanying drawing and embodiment, the present invention is further detailed explanation:
Fig. 1 is the process route chart of micro-algae Direct Hydrothermal Hydrogenation for chemical method.
Embodiment
The present invention proposes a kind of is the method for raw material Direct Hydrothermal Hydrogenation for chemical by reproducible micro-algae, and its process route chart can be as shown in Figure 1.The key step of the method is as follows:
Rich sugared micro-algae is after collection centrifugal concentrating, add together with water by a certain percentage in hydrogenator, add again a certain amount of catalyzer with hydrogenation hydrogenolysis activity, carry out hydrogenation hydrogenolysis, after reaction finishes, product, after a series of processing such as centrifugal, underpressure distillation, rectifying, absorption, can obtain carbonatoms and be 2～6 multiple glycol products and important intermediate hydroxyacetone etc., and catalyzer after drying recyclable regenerative uses.
Below by specific embodiment, the present invention is described further.Should be understood that the only non-limiting scope of the present invention for the present invention is described of following examples.
In addition, the hydrogenation catalyst relating in following examples can be the conventional catalyzer with hydrogenation hydrogenolysis activity, as can be a kind of in loaded catalyst and unsupported catalyst or their combination.Wherein, the carrier of loaded catalyst can be the one in gac (AC), diatomite, aluminum oxide or zeolite molecular sieve.
Furtherly, preferably adopt following catalyzer:
The active ingredient of catalyzer is group VIII metal element and subgroup metallic element; Wherein, group VIII metal element is Ni, Ru or Pt; Subgroup metallic element is Cu, Zn, Cr, Mo or W.
Embodiment 1
In the Parr autoclave that experiment is 100ml at volume, carry out, and operate in mode intermittently.First in reactor, add 0.5g grid algae and 50ml deionized water, solid-to-liquid ratio is 1g:100mL, and wherein, the carbohydrate content of grid algae is 60.15%(mass percent), N content: 0.006%(mass percent), S content: 0.08%(mass percent).Add after 0.15g hydrogenation catalyst (having the catalyzer of hydrogenation hydrogenolysis activity) again, by reactor sealing, pass into air in High Purity Hydrogen displacement still, and keep hydrogen initial partial pressure to be set as 4MPa, mixing speed is controlled at 600r/min.After heating starts, temperature is raised to 280 DEG C with the speed of 15K/min, and reaction 30min, stops heating, be cooled to after room temperature, carefully collecting reaction product, goes out liquid product and solid catalyst by centrifugation, and liquid product is after 0.25 μ m micro-filtration head filters, carry out GC-MS, GC-FID, LC qualitative and quantitative analysis, catalyzer is after soaked in absolute ethyl alcohol, and forced air drying 12h in 120 DEG C of baking ovens, circulates for subsequent use.
With this understanding, grid algae hydrothermal conversion rate reaches 95.4%(mass percent, lower same), wherein, 1,2-PD yield reaches 15.76%(mass percent, lower same), ethylene glycol is 8.34%(mass percent, lower same), hydroxyacetone is 27.84%(mass percent, lower same).
Embodiment 2
Specific implementation process is as embodiment 1, and difference is to add 10g grid algae and 50ml deionized water, and solid-to-liquid ratio is 20g:100mL, adds 2.0g hydrogenation catalyst simultaneously; Temperature of reaction is stabilized in 250 DEG C, and the reaction times extends to 2h, and hydrogen initial partial pressure is set in 8MPa.
After reaction finishes, product analysis learns, grid algae hydrothermal conversion rate reaches 100%, and wherein, 1,2-PD yield reaches 9.32%, and ethylene glycol is 7.86%, and hydroxyacetone is 30.66%.
Embodiment 3
Specific implementation process is as embodiment 1, and difference is that the raw material adding is chlorella, and the carbohydrate content of chlorella is 50.24%, N content: 0.008%, S content: 0.07%.The chlorella quality adding is 5g, and deionized water is 50ml, and solid-to-liquid ratio is 10g:100mL, and add quality is the hydrogenation catalyst of 1.0g simultaneously; System temperature is down to 150 DEG C, and the reaction times extends to 4h, and hydrogen initial partial pressure is set in 6MPa.
After reaction finishes, product analysis learns, chlorella hydrothermal conversion rate reaches 78.36%, and wherein, 1,2-PD yield reaches 10.34%, and ethylene glycol is 13.46%, and hydroxyacetone is 35.42%.
Embodiment 4
Specific implementation process is as embodiment 1, and difference is that the raw material adding is salt algae, and the carbohydrate content of salt algae is 40.67%, N content: 0.009%, S content: 0.10%.The salt algae quality adding is 2.5g, and deionized water is 50ml, and solid-to-liquid ratio is 5g:100mL, and add quality is the hydrogenation catalyst of 0.5g simultaneously; Temperature of reaction maintains 250 DEG C, and the reaction times is 2h, and hydrogen initial partial pressure is set in 4MPa.
After reaction finishes, product analysis learns, salt algae hydrothermal conversion rate reaches 100%, and wherein, 1,2-PD yield reaches 6.68%, and ethylene glycol is 8.53%, and hydroxyacetone is 18.11%.
Embodiment 5
Specific implementation process is as embodiment 1, and difference is the chlamydomonas that adds 0.5g, and the carbohydrate content of chlamydomonas is 45.39%, N content: 0.007%, S content: 0.08%.Deionized water is 50ml, and solid-to-liquid ratio is 1g:100mL, and add quality is the hydrogenation catalyst of 0.15g simultaneously; Temperature of reaction maintains 250 DEG C, and the reaction times is 1h, and hydrogen initial partial pressure is set in 4MPa.
After reaction finishes, product analysis learns, chlamydomonas hydrothermal conversion rate reaches 92.31%, and wherein, 1,2-PD yield reaches 12.62%, and ethylene glycol is 8.58%, and hydroxyacetone is 27.84%.
Embodiment 6
Specific implementation process is as embodiment 1, and difference is the Chlorococcum that adds 1.0g, and the carbohydrate content of Chlorococcum is 52.45%, N content: 0.005%, S content: 0.06%.Deionized water is 50ml, and solid-to-liquid ratio is 2g:100mL, and add quality is the hydrogenation catalyst of 0.2g simultaneously; Temperature of reaction maintains 200 DEG C, and the reaction times is 2h, and hydrogen initial partial pressure is set in 6MPa.
After reaction finishes, product analysis learns, Chlorococcum hydrothermal conversion rate reaches 98.36%, and wherein, 1,2-PD yield reaches 10.01%, and ethylene glycol is 6.53%, and hydroxyacetone is 34.28%.
Embodiment 7
In micro-algae hydro-thermal shortening trickle bed catalyst test apparatus that experiment is 10ml at volume continuously, carry out.First preparing solid-to-liquid ratio is the grid algae slurries of 1g:50ml, and compound method, for grid algae and water are mixed by a certain percentage, by powerful mechanical stirring, to micron order, is transferred to charging stock tank by slurry agitation, is preheated to 50 DEG C.Hydrogenation catalyst is through compression molding, and fragmentation, accurately weighs 10g after sieving, and the flat-temperature zone being filled in trickle bed reaction tubes is evaluated.The carrier gas of experiment is N2 and H2, is 4MPa by regulating keeping system pressure, and wherein, hydrogen is 1MPa, and nitrogen is 3MPa.After reaction starts, the flow of grid algae slurry feed is 2ml/min, and the temperature of catalyzer flat-temperature zone remains on 300 DEG C, after question response is steady, analyzes every 15min sampling.Product analysis method is with reference to embodiment 1.
With this understanding, grid algae hydrothermal conversion rate reaches 80.23%, and wherein, 1,2-PD yield reaches 11.76%, and ethylene glycol is 7.86%, and hydroxyacetone is 20.12%.
The present invention is directed to Wooden Biomass raw material growth cycle slow, take up an area large, biomass is lower and be subject to the realistic problems such as seasonal effect is larger, take the lead in proposing the not treated Direct Hydrothermal hydrogenation of a kind of micro-algae hydrogenolysis and prepared the method for dibasic alcohol, the growth cycle of micro-algae is short, fecundity is strong, easily possessionization is cultivated, adaptive capacity to environment is strong, contains abundant carbohydrate generally more than 50% in micro-algae, and prerequisite that provides of preparation bio-based dibasic alcohol is all provided for it for these; Micro-algae only needs simple collection concentrated without the dry reaction raw materials that just can be used as, the characteristic that makes full use of water realizes micro-algae hydrolysis, hydro-thermal hydrogenation catalyst hydrogenolysis one step completes, in process without acid/alkali and enzymic hydrolysis process, should " one kettle way " technique simple and green non-pollution, high and the good product selectivity of feed stock conversion, catalyzer is renewable use after simple solid-liquid separation, has advantage and the actual application value of realization.
Claims (10)
1. micro-algae Direct Hydrothermal Hydrogenation, for a method for chemical, is characterized in that, comprises step:
In reactor, add algae and water in a subtle way, and have under the catalyst action of hydrogenation hydrogenolysis activity, carry out hydrogenation hydrogenolysis 10～360min in 150～300 DEG C, obtain chemical.
2. the method for claim 1, is characterized in that: described reactor is intermittent type or flow reactor.
3. the method for claim 1, is characterized in that: described micro-algae comprises: the micro-algae of fresh water or seawater;
The solid-to-liquid ratio of micro-algae and water is 1g:100mL～50g:100mL.
4. method as claimed in claim 3, is characterized in that: described micro-algae comprises: one or more in grid algae, chlorella, salt algae, chlamydomonas, Chlorococcum.
5. the method as described in claim 3 or 4, is characterized in that: the mass content of the carbohydrate of described micro-algae is 40～65%, and the mass content of nitrogen is 0～0.5%, and the mass content of sulphur is 0～0.5%.
6. the method for claim 1, is characterized in that: described catalyzer comprises: a kind of in loaded catalyst and unsupported catalyst or their combination.
7. method as claimed in claim 6, is characterized in that: the active ingredient of described catalyzer comprises: group VIII metal element and subgroup metallic element;
Wherein, group VIII metal element comprises: Ni, Ru or Pt; Subgroup metallic element comprises: Cu, Zn, Cr, Mo or W;
The carrier of loaded catalyst comprises: gac, diatomite, aluminum oxide or zeolite molecular sieve.
8. the method for claim 1, is characterized in that: in described hydrogenation hydrogenolysis, the original pressure of hydrogen is 1.0～8.0MPa.
9. the method for claim 1, is characterized in that: described chemical comprises: the dibasic alcohol that carbonatoms is 2～6 and hydroxyacetone.
10. the method for claim 1, is characterized in that: described catalyzer through solid-liquid separation, dry after, can use by cyclic regeneration.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831323A (en) * | 2017-02-27 | 2017-06-13 | 中国科学院上海高等研究院 | It is a kind of by corncob Direct Hydrothermal Hydrogenation for chemicals method |
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| CN101768050A (en) * | 2009-12-25 | 2010-07-07 | 北京大学 | Method for preparing ethylene glycol and 1,2-propylene glycol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831323A (en) * | 2017-02-27 | 2017-06-13 | 中国科学院上海高等研究院 | It is a kind of by corncob Direct Hydrothermal Hydrogenation for chemicals method |
| CN106831323B (en) * | 2017-02-27 | 2020-06-05 | 中国科学院上海高等研究院 | Method for preparing chemicals by direct hydrothermal hydrogenation of corncobs |
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