CN106397495A - Hydrogenation degradation product of lignin and hydrogenation degradation method of lignin - Google Patents
Hydrogenation degradation product of lignin and hydrogenation degradation method of lignin Download PDFInfo
- Publication number
- CN106397495A CN106397495A CN201610789363.7A CN201610789363A CN106397495A CN 106397495 A CN106397495 A CN 106397495A CN 201610789363 A CN201610789363 A CN 201610789363A CN 106397495 A CN106397495 A CN 106397495A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- acid
- lignin
- catabolite
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a hydrogenation degradation product of lignin and a hydrogenation degradation method of lignin. The softening point of the hydrogenation degradation product of the lignin is 40-150 DEG C, and the dissolution rate of per 10mL of ethanol to 1g of the hydrogenation degradation product under 70 DEG C is 60%-99.5%. Compared with the existing product, the hydrogenation degradation product provided by the invention is low in molecular weight, narrow in distribution range and higher in application value.
Description
Technical field
The present invention relates to technical field of biomass resource utilization, especially relate to the hydrogenation catabolite of lignin and wooden
The hydrogenation biodegrading process of element.
Background technology
Tellurian resource is the basis that human society has with development, and it includes mineral resources and biomass resource.Ore deposit
Goods and materials source is non-renewable resources, is the fossil resource that each geologic(al) period that the earth develops at it is formed.Oil, natural gas and
Coal is carbon fossil resource, is the main energy form of human society, also directly or indirectly provides in a large number for human society
Chemicals and basic material.Metalliferous mineral and inorganic salts material are to we provide raw metal, pottery, construction material, base
The basic raw materials such as plinth chemicals.In existing resource consumption structure, a large amount of exploitations of mineral resources are to environment and ecological peace
Entirely do great damage.A large amount of burnings of Fossil fuel cause substantial amounts of carbon dioxide, nitrogen oxides, sulfur-containing compound, with much money
The discharge such as genus, thus causes the serious environmental problems such as greenhouse effect, acid rain, haze, ocean eutrophication.Mineral resources
For non-renewable, the upper reserves of the earth and amount usable are limited, because human society is at present to this kind of limited resources
Irreplaceable huge dependency, human society is faced with unprecedented survival and development crisis.Resource, the energy, environment are asked
Topic is a quagmire of human social, and by contrast, institute of China facing challenges are more severe.Because population is many
Many, economic development pressure is huge, and resource is relatively deficient and utilization rate is low, therefore, develops the alternate resources of sustainable use and carries
The utilization rate of high resource has become one of China's key problem in the urgent need to address.
In a broad sense, the sun is the earth uniquely renewable and continual energy source, and specific form of energy includes
Photoelectricity, photo-thermal, water potential energy, wind energy equal energy source form.And can be exactly uniquely biomass as physical resources, biomass refer to
The various organisms being produced by photosynthesis.The biomass of broad sense include all plants, microorganism and all with plant and
Microorganism is the animal of food.But in actual application, we are more likely to refer to biomass in agriculture and forestry production process and produce
The garbage producing in raw lignocellulose garbage and Processing Farm Produce.By the photosynthesis of plant, on the earth
The annual biomass gross mass producing can reach more than surprising hundred billion ton, can absorb and fix 56,400,000,000 tons of carbon, stores 310
The solar energy of hundred million kilojoules.Biomass not only provide human foods, and are uniquely can to regenerate on a large scale on the earth and enough to support
Organic carbon resource of human social development demand.The U.S. proposes " biomass Technology Roadmap " it is desirable to accelerate to improve U.S. within 2002
State develops biomass energy and the ability of biomass-based product.In April, 2012, U.S. government issued《National biological economy blueprint》, carry
Go out " setting up and develop biomass resource sustainable use, the biological economy based on biotechnology ".European Union issues Europe in 2008
Alliance's strategy energy technology plan, proposes to strengthen the technical research of biomass energy, puies forward L competitiveness.Australia also formulates for 2009
?《Regenerative resource target》, determine the year two thousand twenty by the ratio in electric power output Bao Kuo the Renewable resource including biomass
Bring up to 20%.The Chinese government also pays much attention to the exploitation of biomass resource utilization technology, has successively put into effect a series of strategy rule
Draw.Formulate within 2007《National Long-and Medium-term Development planning outline》With《Regenerative resource Long-and Medium-term Development is planned》.Chinese science
The research groups of institute, Chinese Academy of Engineering and correlation respectively to biomass resource using being made that corresponding strategical planning and carry
Go out route map.
Biomass resource main component is cellulose, hemicellulose, lignin, and wherein lignin is uniquely to contain aromatic hydrocarbons list
The natural polymer of unit, reserves are only second to cellulose it is considered to be a kind of following important green resource.Lignin mainly quilt at present
As garbage, it is present in paper industry, the black liquor of biomass refining generation after isolating cellulose or hemicellulose.Effectively
Utilization Liginon Resource can be chemical industry provide reproducible raw material, also can solve the pollution to environment for the black liquor simultaneously.
Due to the complexity of this body structure of lignin and property, and isolate and purify brought high cost from black liquor, to lignin
The research of efficient application method is weaker.
Content of the invention
The first object of the present invention is to provide a kind of hydrogenation catabolite of lignin, and this product is compared existing product and divided
Son amount is low, and narrow distribution range, and using value is higher.
The second object of the present invention is to provide a kind of hydrogenation biodegrading process of lignin, described method Degradation and Transformation rate
Height, the low-molecular-weight molecule accounting obtaining is high, low cost, and production efficiency is high.
In order to solve above technical problem, the invention provides technical scheme below：
A kind of hydrogenation catabolite of lignin, the softening point of described hydrogenation catabolite is 40-150 DEG C, every 10mL second
Alcohol is 60%-99.5% to hydrogenation dissolution rate at 70 DEG C for the catabolite described in 1g.
It is low that this product compares existing product molecular weight, and narrow distribution range, and using value is higher.
Preferably, every 10mL ethanol is 70%-97% to hydrogenation dissolution rate at 70 DEG C for the catabolite described in 1g, more excellent
Select 80%-95%.
The softening point of described hydrogenation catabolite is preferably 50 DEG C -140 DEG C, further for 60-130 DEG C.
Preferably, in every gram of described hydrogenation catabolite, content of phenolic hydroxyl groups is 3mmol-8mmol, preferably 4.0mmol-
6.5mmol.
Preferably, the weight average molecular weight of described hydrogenation catabolite is 800-2000, more preferably 1000-1600.
This product is mainly with the black liquor containing lignin as raw material, carries out hydrogenation degraded anti-in the presence of hydrogenation catalyst
Should, it is obtained.
The solid contents of described black liquor are preferably 30wt%～50wt%；
Preferably, the active component of described hydrogenation catalyst includes at least nickel, preferably also comprises copper, aluminum, zinc, appointing in chromium
Anticipate the combination of one or more.
Promoter can be introduced on this basis, it is to avoid the operation of separating-purifying lignin.Promoter mainly by with
Lower one-tenth is grouped into：By weight,
35～50 parts of polyhydroxy fragrant race carboxylic acid,
25～40 parts of polyhydric phenols.
In prior art, the catalyst used by hydrogenation lignin degrading is all single component, is usually loaded with metal and lives
The catalyst of property component it is impossible to be directly used in black liquor it is necessary to first by lignin from black liquor separating-purifying out, competence exertion
Catalytic action.And the promoter that the present invention provides, on the one hand directly enhance the activity of hydrogenation catalyst, on the one hand reduce
The interference that in black liquor, impurity reacts to lignin degradation.Therefore, the promoter of the present invention is permissible after combining with hydrogenation catalyst
It is directly used in the hydrogenation degradation reaction of lignin in black liquor.
Described polyhydroxy fragrant race carboxylic acid is preferably 2,4- resorcylic acid, 3,5- resorcylic acid, 2,6- dihydroxy
In in yl benzoic acid, Gallic Acid, diphenolic acid one or several, more preferably diphenolic acid.
One or more of the preferred Pyrogentisinic Acid of described polyhydric phenols, a phenol, o-phenyl phenol, phloroglucinol, naphthols, anthrol,
More preferably Pyrogentisinic Acid.
Above-mentioned composition can improve in the following areas：
Described promoter also includes 5～10 portions of nonionic surfactants, and/or 10～15 parts of phenolphthalein.
Nonionic surfactant can improve the promoter and hydrogenation catalyst dispersibility in Black Liquor System and
The compatibility, thus improve catalytic efficiency.Phenolphthalein can improve the compatibility between each component of promoter, improves cooperative effect.
Described nonionic surfactant is preferably OPEO, NPE, fatty acid polyglycol
One or more of oxygen vinyl acetate, high-carbon fatty alcohol polyoxyethylene ether, tween, preferably NPE, octyl phenol
One or more of polyoxyethylene ether, more preferably polyoxyethylene ether TX-15.
Polyhydroxy fragrant race carboxylic acid, the weight ratio more preferably 35～45 of polyhydric phenols：25～40.
After introducing nonionic surfactant, phenolphthalein, proportioning is preferably：
The promoter of hydrogenation catalyst and the present invention is with 1～10：0.1～7 weight than with the use of when, catalytic effect
More preferably, preferably 5-7：3.
As described above, the promoter of the present invention needs to be used in conjunction with hydrogenation catalyst, and the hydrogenation that it can coordinate is urged
Agent has multiple, is particularly useful for the hydrogenation catalyst of lignin degradation, the present invention is also improved to hydrogenation catalyst：
Hydrogenation catalyst is preferably：Add alkali liquor in the mixed liquor mainly contain following density component, reaction is obtained：
Nickel salt 0.1～1.0mol/L, preferably 0.1～0.6mol/L；
Acylate 0.01～the 0.3mol/L of magnetic metal,
Hypophosphorous acid and/or hypophosphites 0.12～2.0mol/L, preferably 0.2～2.0mol/L.
When containing hypophosphorous acid and hypophosphites in raw material simultaneously, concentration refers to both summations.
This catalyst has higher magnetic, can be recycled by magnetic recovery device or Magnet, the joining of each raw material
5 mechanism are substantially：In the presence of alkali, nickel salt, the acylate of magnetic metal form polynary co-precipitate, and in hypophosphorous acid
And/or in the presence of hypophosphites, it is reduced into metal simple-substance, and nickel therein is the main active component of catalyst, other magnetic
Property metal can increase its magnetic it is ensured that hybrid particles can be adsorbed completely by magnetic recovery device.
The cycle-index of described catalyst is more than 13 times.
Described nickel salt is the precursor of magnetic recovery hydrogenation catalyst main active component, and they are mainly water miscible,
Preferably nickel salt is selected from Nickel dichloride., nickel sulfate, nickel formate, nickel acetate, citric acid nickel, wherein most preferably nickel acetate.
The preferred ferrum of described magnetic metal, and/or cobalt；One of described organic acid preferred fatty acid, hydroxy acid, aminoacid
Or multiple, one or more of optimization citric acid, acetic acid, acetic acid；
Described magnetic metal optimization citric acid ferrum and cobalt acetate；In described mixed liquor, the concentration of ferric citrate is preferably 0.01
～0.1mol/L, more preferably 0.01～0.06mol/L；In described mixed liquor, the concentration of cobalt acetate is preferably 0.025～0.3mol/
L.
Described hypophosphorous acid and hypophosphites are reducing agent, and its Main Function is progressively by precipitated metal under conditions of heating
Reduction forms hybrid particles, the wherein alkali metal salt of most preferably hypophosphorous acid.
The preferred highly basic of described alkali, most preferably sodium hydroxide it is proposed that adding as a solution, sodium hydroxide solution dense
Degree is preferably 200g/L.
Preferably, described mixed liquor also contains saccharide compound, the Main Function of described saccharide compound be dispersion and
Stablize the Diversity precipitate particles of initial stage formation, and within the scope of holding it in certain granular size, be preferably selected from
One or more of xylose, Fructose, sucrose, Lactose, glucose.Wherein most preferably glucose.Saccharide compound dense
Degree preferably 0.01～0.05mol/L, preferably 0.02～0.05mol/L.
Above-mentioned catalyst preferably formula is：Nickel salt, ferric citrate, cobalt acetate, saccharide compound, hypophosphorous acid and/or secondary
Phosphate forms catalyst.In described catalyst raw material, each composition can use any amount in its concentration range, and nickel salt is preferred
0.1～0.8mol/L, 0.1～0.6mol/L；Ferric citrate preferably 0.01～0.06mol/L；Cobalt acetate preferably 0.15～
0.3mol/L, 0.025～0.3mol/L；Saccharide compound preferably 0.02～0.05mol/L；Hypophosphorous acid and/or hypophosphites are excellent
Select 0.2～2.0mol/L.
Described catalyst can be form or the solid particle of dirty solution, and preferably the catalysis activity of the latter is high,
The preferably pH in the manufacture of described alkali is the black precipitate being formed in the environment of 10-13, and specific preparation method is：
By the composition mixing in addition to alkali, it is gradually added sodium hydroxide afterwards, until the pH of solution is 10-13, then side heating
At least 45min is stirred on side, now can generate black precipitate, afterwards with washing solid to neutrality, then with magnet adsorption, obtains final product solid
Catalyst.
Wherein alkali liquor adds under agitation, and the temperature of reaction is preferably 55-95 DEG C；Preferably, described alkali liquor is dense
Spend for 200-250g/L；It is furthermore preferred that the speed of described stirring is more than 600 revs/min.
Described hydrogenation catalyst particle diameter is preferably less than 5 μm, and particle diameter is less, and specific surface area is bigger, and catalysis activity is higher.
Described hydrogenation catalyst is preferably amorphous state.Amorphous forward direction being randomly distributed more conducively degradation reaction is entered
OK, improve reaction rate.Mainly by nickel acetate, direct reaction obtains amorphous nickel boron alloy powder in aqueous with sodium borohydride
, in order to keep its activity, it is generally stored in water.
In the method for catalytic hydrogenation lignin degrading, the weight of described hydrogenation catalyst and lignin is than preferably 7.5-
10：300, higher Degradation and Transformation rate can be obtained.
The condition of catalytic hydrogenation degradation reaction is preferably：150-250 DEG C, Hydrogen Vapor Pressure be 2.0～8.0MPa；More preferably
150～220 DEG C, Hydrogen Vapor Pressure be 5.0～6.0MPa, or 190～220 DEG C, Hydrogen Vapor Pressure be 4.5～6.0MPa；To obtain
Higher Degradation and Transformation rate and the product of more low-molecular-weight.
Compared with prior art, the present invention achieves following technique effect：
(1) investigated a kind of hydrogenation catabolite of Novel wooden quality, this product using value is higher, and range of application is more
Extensively, can be used for adhesive and the plastic applications that can degrade；
(2) invented a kind of carbon monoxide-olefin polymeric being used directly for black liquor, the regeneration for lignin is opened up
New way；Decrease substantial amounts of discharge of wastewater, decrease operation link simultaneously, save production cost；
(3) promoter, with coordinating for lignin degrading with hydrogenation catalyst, can obtain higher Degradation and Transformation rate
Height, and low-molecular-weight accounting.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is clearly and completely described, but ability
Field technique personnel will be understood that, following described embodiment is a part of embodiment of the present invention, rather than whole embodiments,
It is merely to illustrate the present invention, and be not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.Unreceipted actual conditions person in embodiment, the condition according to normal condition or manufacturer's suggestion is carried out.Agents useful for same or instrument
Unreceipted production firm person, being can be by the commercially available conventional products bought and obtain.
Hereafter average ethanol dissolving ratio refers to：Every 10mL ethanol is hydrogenated with dissolution rate at 70 DEG C for the catabolite to 1g.Phenol
Hydroxy radical content refers both to contained phenolic hydroxyl group amount in every gram of product.
Embodiment 1 to 5
The formula of the catalyst of five embodiments is as shown in table 1.
The preparation method of catalyst is：
Respectively according to each concentration of component specified in table 1 below by nickel acetate, ferric citrate, cobalt acetate, sodium hypophosphite and
Glucose is dissolved in deionized water, is gradually added the sodium hydroxide solution of 20% (i.e. 200g/mL) in above solution, is formed
Nickel hydroxide-hydrated ferric oxide .-cobalt hydroxide ternary mixed sediment is so that the pH value of final mixture aqueous solution part is not less than
10.The adition process of sodium hydroxide solution, needs constantly to stir, and the rotating speed of stirring is 600 revs/min.Then above is mixed
Compound is further heated to 95 DEG C of reaction treatment and is no less than 45 minutes.With the carrying out of reaction, can progressively release gas and be formed
The precipitate of black, is enriched with black solid product with Magnet and is washed with water to neutrality, that is, magnetic recovery catalyst is obtained.
The catalytic hydrogenation degradation reaction of lignin：
1) black liquid being configured to weight content is 30% (300g/L), the reactant liquor of sodium hydroxide 8% (80g/L)；
2) add 7.5 grams of the catalyst being obtained above in every liter of reactant liquor, every liter of reactant liquor adds 3 grams of promoter
(mix by weight percentage, NPE (TX-15) 9%, diphenolic acid 40%, Pyrogentisinic Acid 40%, phenolphthalein
11%), it is placed in hermetic container, after being filled with Hydrogen Vapor Pressure 5.0MPa, stirred with the rotating vane that rotating speed is 200 revs/min at 180 DEG C
Mix reaction 4 hours；
3) reacted mixture utilizes the sedimentation method to remove hydrogenation catalyst, carries out acid out with sulphuric acid complete to lignin solid
Portion separates out, and the concentration using sulphuric acid is 40%, and lignin degrading solid by filtration that acid out obtains is collected, washed with clear water to
PH value 5, obtains lignin degrading pressed powder after being dried.
4) degradation products are evaluated：
600～1200, the oligomeric lignin molecule being in this scope can be completely dissolved the molecular weight of lignin degrading
In ethanol, and can not be dissolved in ethanol without the lignin molecule of degraded.In order to clearly assess catalytic degradation method
Effectiveness, needs to define two crucial measurement indexs：Degradation and Transformation rate (%) and ethanol dissolving ratio (%).Degradation and Transformation rate
Refer to the ratio that lignin degrading accounts for overall reaction lignin amount, ethanol dissolving ratio refers to lignin degrading middle-molecular-weihydroxyethyl and is less than 1200 products
The ratio of thing,
Its specific assay method is：Take 1 gram of lignin degrading to be dissolved in 10 milliliters of ethanol and be heated to 70 DEG C, isolate not
Dissolved solid, calculates the ratio that dissolving part accounts for total degradation lignin.This index can simply and effectively evaluate catalysis fall
The efficiency of solution preocess.
The degradation results of five embodiments are as shown in table 2.
The catalyst formulation of table 1 embodiment 1-5
| The each concentration of component of catalyst preparation (mol/L) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Nickel acetate | 0.1 | 0.6 | 1.0 | 0.6 | 0.6 |
| Ferric citrate | 0.01 | 0.06 | 0.1 | 0.01 | 0.1 |
| Cobalt acetate | 0.3 | 0.15 | 0.01 | 0.15 | 0.15 |
| Sodium hypophosphite | 0.2 | 0.12 | 2.0 | 0.12 | 0.12 |
| Glucose | 0.05 | 0.02 | 0.01 | 0.02 | 0.02 |
The degradation results of table 2 embodiment 1-5
| Catalytic performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Average ethanol dissolving ratio (%) | 82 | 90 | 74 | 85 | 80 |
| Cycle-index | 21 | 29 | 18 | 17 | 25 |
| Product softening point DEG C | 85-87 | 65-67 | 123-125 | 72-74 | 88-90 |
| Content of phenolic hydroxyl groups mmol | 4.72 | 5.67 | 3.82 | 5.02 | 4.53 |
| Weight average molecular weight | 1424 | 1321 | 1575 | 1366 | 1457 |
Embodiment 6-7
Embodiment 6-7 and differing only in of embodiment 1 replace nickel acetate with Nickel dichloride. or nickel sulfate, in table 3 respectively
List test result.
The degradation results of table 3 embodiment 6-7
| Catalytic performance | Embodiment 6 | Embodiment 7 |
| Average ethanol dissolving ratio (%) | 72 | 71 |
| Cycle-index | 21 | 15 |
| Product softening point DEG C | 128-130 | 130-132 |
| Content of phenolic hydroxyl groups mmol | 3.57 | 3.43 |
| Weight average molecular weight | 1625 | 1650 |
Embodiment 8-11
Embodiment 8-11 and differing only in of embodiment 1 replace glucose with xylose, Fructose, sucrose or Lactose respectively,
List test result in table 4.
The degradation results of table 4 embodiment 8-11
| Catalytic performance | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| Average ethanol dissolving ratio (%) | 90 | 87 | 85 | 81 |
| Cycle-index | 26 | 22 | 18 | 15 |
| Product softening point DEG C | 65-67 | 70-72 | 72-74 | 86-88 |
| Content of phenolic hydroxyl groups mmol | 5.67 | 5.23 | 5.02 | 4.65 |
| Weight average molecular weight | 1315 | 1337 | 1373 | 1443 |
Embodiment 12
Identical with the catalyst of embodiment 1, but the method for lignin degrading is different, is only that reaction temperature is different, this reality
Apply example and be 250 DEG C, its degradation results is as shown in table 7.
The degradation results of table 7 embodiment 12
| Catalytic performance | Embodiment 12 |
| Average ethanol dissolving ratio (%) | 96 |
| Product softening point DEG C | 54-56 |
| Content of phenolic hydroxyl groups mmol | 6.34 |
| Weight average molecular weight | 1128 |
Embodiment 13
Identical with the catalyst of embodiment 1, but the method for lignin degrading is different, is only that Hydrogen Vapor Pressure is different, this reality
Applying example is 6.0MPa, and its degradation results is as shown in table 8.
The degradation results of table 8 embodiment 13
| Catalytic performance | Embodiment 13 |
| Average ethanol dissolving ratio (%) | 93 |
| Product softening point DEG C | 59-61 |
| Content of phenolic hydroxyl groups mmol | 5,89 |
| Weight average molecular weight | 1216 |
Embodiment 14
Identical with the catalyst of embodiment 1, but the method for lignin degrading is different, is only that lignin and hydrogen in reactant liquor
The concentration of sodium oxide is different, and the concentration of the present embodiment sodium hydroxide is 100g/L, and lignin concentration is 350g/L, its degradation results
As shown in table 9.
The degradation results of table 9 embodiment 14
| Catalytic performance | Embodiment 14 |
| Average ethanol dissolving ratio (%) | 85 |
| Product softening point DEG C | 72-74 |
| Content of phenolic hydroxyl groups mmol | 5.08 |
| Weight average molecular weight | 1386 |
The hydrogenation catalyst that hereafter all embodiments are adopted is all same as Example 2.
Embodiment 15-22
Black liquor source used by embodiment 15-22 is different, respectively from larch, cizu, bagasse, Caulis et Folium Oryzae, wheat straw, cotton
The black liquor that stalk produces for raw material papermaking, and the black liquor of corn cob refining xylose, the black liquor of straw bio-ethanol；But it is used
Carbon monoxide-olefin polymeric and hydrogenation degradation technique are identical, specific as follows：
By 3 liters of black liquor (admittedly containing 43%), 5 grams of hydrogenation catalysts, 3 grams of promoters (mix, nonyl by weight percentage
Base phenol polyethenoxy ether (TX-15) 8%, diphenolic acid 40%, Pyrogentisinic Acid 40%, phenolphthalein 12%) be sealed in agitator and add
In 10 liters of stainless steel reactors of hot device.
Then by reactor nitrogen displacement three times, with hydrogen exchange twice, being filled with Hydrogen Vapor Pressure is 4.5MPa.To react
Mixture is heated up, and stirring at a temperature of 190 DEG C carries out catalytic reaction.Speed of agitator is 200 revs/min.Catalytic degradation is anti-
Should carry out 2.5 hours.After completing catalytic degradation reaction, progressively empty remaining hydrogen.After filtering out Hydrogenation catalyst granule, right
Reactant mixture 40% sulphuric acid carries out acid out and all separates out to lignin solid.The lignin degrading solid that acid out obtains passes through
It is collected by filtration, washed with clear water to pH value 5, after being dried, obtain lignin degrading pressed powder.
The result of eight embodiments such as table 10 below.
The black liquor catalytic degradation result of table 10 different material
Embodiment 23-29
Response time used by embodiment 23-29, temperature and Hydrogen Vapor Pressure are all different, as shown in table 2, catalyst used
And other process conditions all same, as follows：
By 3 liters of black liquor (admittedly containing 43%), 5 grams of nickel boron hydrogenation catalysts, 3 grams of promoter (NPEs
(TX-15) 8%, diphenolic acid 40%, Pyrogentisinic Acid 40%, phenolphthalein 12%) be sealed in agitator and heater 10 liters stainless
In steel reactor.
Then by reactor nitrogen displacement three times, with hydrogen exchange twice, being filled with Hydrogen Vapor Pressure is 3.0～6.0MPa.
Reactant mixture is heated up, stirring at a temperature of 150 DEG C～220 DEG C carries out catalytic reaction.Speed of agitator be 200 turns/
Point.Catalytic degradation reaction carries out 1.5～3 hours.After completing catalytic degradation reaction, progressively empty remaining hydrogen.Filter out and add
After hydrogen catalyst granule, with 40% sulphuric acid, acid out is carried out to reactant mixture and all separates out to lignin solid.Acid out obtains
Lignin degrading solid by filtration is collected, and is washed with clear water to pH value 5, obtains lignin degrading pressed powder after being dried.
Degradation results such as table 11.
Table 11
Embodiment 30-34
Catalyst used by embodiment 30-34 is different from promoter proportioning, and as shown in table 12, other process conditions are complete
Exactly the same, as follows：
By 3 liters of black liquor (admittedly containing 43%), 3～7 grams of nickel boron hydrogenation catalysts, 1～3 gram of promoter (polyoxyethylene nonyl phenyl second
Alkene ether (TX-15) 8%, diphenolic acid 40%, Pyrogentisinic Acid 40%, phenolphthalein 12%) be sealed in agitator and heater 10 liters
In stainless steel reactor.
Then by reactor nitrogen displacement three times, with hydrogen exchange twice, being filled with Hydrogen Vapor Pressure is 4.5MPa.To react
Mixture is heated up, and stirring at a temperature of 190 DEG C carries out catalytic reaction.Speed of agitator is 200 revs/min.Catalytic degradation is anti-
Should carry out 2.5 hours.After completing catalytic degradation reaction, progressively empty remaining hydrogen.After filtering out Hydrogenation catalyst granule, right
Reactant mixture 40% sulphuric acid carries out acid out and all separates out to lignin solid.The lignin degrading solid that acid out obtains passes through
It is collected by filtration, washed with clear water to pH value 5, after being dried, obtain lignin degrading pressed powder.
Degradation results such as table 12.
Table 12
The formula of the promoter used by embodiment 35-38 embodiment 35-38 is different, remaining process conditions all same, such as
Under：
By 3 liters of black liquor (admittedly containing 43%), 5 grams of nickel boron hydrogenation catalysts, 3 grams of promoters are sealed in agitator and add
In 10 liters of stainless steel reactors of hot device.
The composition of wherein promoter：
Embodiment 35：NPE (TX-15) 5%；Diphenolic acid 45%；Pyrogentisinic Acid 35%；Phenolphthalein 15%.
Embodiment 36：NPE (TX-15) 10%；Diphenolic acid 35%；Pyrogentisinic Acid 40%；Phenolphthalein 15%.
Embodiment 37：NPE (TX-15) 10%；Diphenolic acid 50%；Pyrogentisinic Acid 25%；Phenolphthalein 15%.
Embodiment 38：NPE (TX-15) 10%；Diphenolic acid 45%；Pyrogentisinic Acid 40%；Phenolphthalein 5%.
Then by reactor nitrogen displacement three times, with hydrogen exchange twice, being filled with Hydrogen Vapor Pressure is 4.5MPa.To react
Mixture is heated up, and stirring at a temperature of 190 DEG C carries out catalytic reaction.Speed of agitator is 200 revs/min.Catalytic degradation is anti-
Should carry out 2.5 hours.After completing catalytic degradation reaction, progressively empty remaining hydrogen.After filtering out Hydrogenation catalyst granule, right
Reactant mixture 40% sulphuric acid carries out acid out and all separates out to lignin solid.The lignin degrading solid that acid out obtains passes through
It is collected by filtration, washed with clear water to pH value 5, after being dried, obtain lignin degrading pressed powder.
Degradation results such as table 13.
Table 13
Finally it should be noted that：Various embodiments above only in order to technical scheme to be described, is not intended to limit；To the greatest extent
Pipe has been described in detail to the present invention with reference to foregoing embodiments, it will be understood by those within the art that：Its according to
So the technical scheme described in foregoing embodiments can be modified, or wherein some or all of technical characteristic is entered
Row equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of lignin hydrogenation catabolite it is characterised in that described hydrogenation catabolite softening point be 40-150 DEG C,
Every 10mL ethanol is 60%-99.5% to hydrogenation dissolution rate at 70 DEG C for the catabolite described in 1g.
2. the hydrogenation catabolite of lignin according to claim 1 is it is characterised in that every 10mL ethanol adds to described in 1g
Dissolution rate at 70 DEG C for the hydrogen catabolite is 70%-97%, preferably 80%-95%；
The softening point of described hydrogenation catabolite is preferably 50 DEG C -140 DEG C, preferably 60-130 DEG C.
3. the hydrogenation catabolite of lignin according to claim 1 is it is characterised in that every gram of described hydrogenation catabolite
Middle content of phenolic hydroxyl groups is 3mmol-8mmol, preferably 4.0mmol-6.5mmol.
4. the hydrogenation catabolite of lignin according to claim 1 is it is characterised in that the weight of described hydrogenation catabolite
Average molecular weight is 800-2000, preferably 1000-1600.
5. the hydrogenation biodegrading process of lignin is it is characterised in that with the black liquor containing lignin as raw material, in the work of hydrogenation catalyst
With under carry out being hydrogenated with degradation reaction, prepared softening point is 40-150 DEG C of hydrogenation catabolite, and every 10mL ethanol is to 1g institute
Stating hydrogenation dissolution rate at 70 DEG C for the catabolite is 60%-99.5%；
The solid contents of described black liquor are preferably 30wt%～50wt%；
Preferably, the active component of described hydrogenation catalyst includes at least nickel, preferably also comprises copper, aluminum, zinc, any one in chromium
Plant or several combinations.
6. the hydrogenation biodegrading process of lignin according to claim 5 is it is characterised in that be hydrogenated with degradation reaction described
It is additionally added promoter；
Described promoter mainly consists of the following composition：By weight, 35～50 parts of polyhydroxy fragrant race carboxylic acid, polyhydric phenols 25
～40 parts；Preferably, 35～45 parts of polyhydroxy fragrant race carboxylic acid；
By weight, described promoter also includes 5～10 portions of nonionic surfactants, and/or 10～15 parts of phenolphthalein；
Described nonionic surfactant is preferably OPEO, NPE, fatty acid polyoxy second
One or more of alkene ester, high-carbon fatty alcohol polyoxyethylene ether, tween, preferably NPE, octyl phenol polyoxy
One or more of vinyl Ether；
Described polyhydroxy fragrant race carboxylic acid is preferably 2,4- resorcylic acid, 3,5- resorcylic acid, 2,6- dihydroxy benzenes
In in formic acid, Gallic Acid, diphenolic acid one or several, more preferably diphenolic acid；
One or more of the preferred Pyrogentisinic Acid of described polyhydric phenols, a phenol, o-phenyl phenol, phloroglucinol, naphthols, anthrol, more excellent
Select Pyrogentisinic Acid；
Preferably, the weight of described hydrogenation catalyst and lignin is than for 7.5-10：300；
The condition of catalytic hydrogenation degradation reaction is preferably：150-250 DEG C, Hydrogen Vapor Pressure be 2.0～8.0MPa；More preferably 150
～220 DEG C, Hydrogen Vapor Pressure be 5.0～6.0MPa, or 190～220 DEG C, Hydrogen Vapor Pressure be 4.5～6.0MPa；Described hydrogenation fall
The time of solution reaction is preferably 1.5～10 hours.
7. lignin according to claim 6 hydrogenation biodegrading process it is characterised in that described promoter mainly by with
Lower one-tenth is grouped into：
8. lignin according to claim 6 hydrogenation biodegrading process it is characterised in that described hydrogenation catalyst with described
The weight of promoter is than for 1～10：0.1～7, preferably 5-7：3；
Described hydrogenation catalyst particle diameter is preferably less than 5 μm, and described hydrogenation catalyst is preferably amorphous state.
9. the hydrogenation biodegrading process of lignin according to claim 5 is it is characterised in that described hydrogenation catalyst is：To
Mainly contain addition alkali liquor in the mixed liquor of following density component, reaction is obtained：
Nickel salt 0.1～1.0mol/L, preferably 0.1～0.6mol/L；
Acylate 0.01～the 0.3mol/L of magnetic metal,
Hypophosphorous acid and/or hypophosphites 0.12～2.0mol/L, preferably 0.2～2.0mol/L；
Described magnetic metal chosen from Fe, and/or cobalt；One of described organic acid preferred fatty acid, hydroxy acid, aminoacid or many
Kind, one or more of optimization citric acid, acetic acid, acetic acid；
Described magnetic metal optimization citric acid ferrum and cobalt acetate；In described mixed liquor the concentration of ferric citrate be preferably 0.01～
0.1mol/L, more preferably 0.01～0.06mol/L；In described mixed liquor, the concentration of cobalt acetate is preferably 0.025～0.3mol/L；
Described nickel salt is preferably one or more of nickel acetate, Nickel dichloride., citric acid nickel, nickel sulfate；
Described hypophosphites are preferably the alkali metal salt of hypophosphorous acid；
Described mixed liquor also contains saccharide compound 0.01～0.05mol/L, preferably 0.02～0.05mol/L；
Described saccharide compound is preferably one or more of xylose, Fructose, sucrose, Lactose, glucose.
10. the hydrogenation biodegrading process of lignin according to claim 9 is it is characterised in that in described hydrogenation degradation reaction
Also include afterwards：
After removing described hydrogenation catalyst, add the sulfuric acid solution acidifying that concentration is 5wt%～60wt%, to the solidss separating out
Carry out filtration washing and obtain final product product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789363.7A CN106397495B (en) | 2016-08-30 | 2016-08-30 | Lignin plus hydrogen catabolite and lignin plus hydrogen biodegrading process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789363.7A CN106397495B (en) | 2016-08-30 | 2016-08-30 | Lignin plus hydrogen catabolite and lignin plus hydrogen biodegrading process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397495A true CN106397495A (en) | 2017-02-15 |
| CN106397495B CN106397495B (en) | 2019-06-18 |
Family
ID=58000574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610789363.7A Active CN106397495B (en) | 2016-08-30 | 2016-08-30 | Lignin plus hydrogen catabolite and lignin plus hydrogen biodegrading process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397495B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294547A (en) * | 2018-10-23 | 2019-02-01 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of displacement of reservoir oil anionic and nonionic amphoteric surfactant and preparation method thereof |
| CN109370633A (en) * | 2018-12-20 | 2019-02-22 | 常州大学 | A kind of lignin adds the method for hydrogen degradation preparation bio oil |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372607A (en) * | 2010-08-11 | 2012-03-14 | 中国科学院大连化学物理研究所 | Method for preparing single benzene ring phenolic compound from alkali lignin |
| CN103232605A (en) * | 2013-05-21 | 2013-08-07 | 济南圣泉集团股份有限公司 | Hydrogenated phenolic pyrolysis lignin and preparation method thereof |
| CN103508858A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compounds employing catalytic cracking of industrial lignins |
| WO2014058686A1 (en) * | 2012-10-08 | 2014-04-17 | Shell Oil Company | Lignocellulosic biomass conversion |
| CN104177223A (en) * | 2013-05-27 | 2014-12-03 | 天津大学 | Application of transition metal phosphide in catalytic conversion of lignin |
| CN104388110A (en) * | 2014-10-29 | 2015-03-04 | 华东师范大学 | Method for preparing chain alkane from lignin |
-
2016
- 2016-08-30 CN CN201610789363.7A patent/CN106397495B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372607A (en) * | 2010-08-11 | 2012-03-14 | 中国科学院大连化学物理研究所 | Method for preparing single benzene ring phenolic compound from alkali lignin |
| CN103508858A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compounds employing catalytic cracking of industrial lignins |
| WO2014058686A1 (en) * | 2012-10-08 | 2014-04-17 | Shell Oil Company | Lignocellulosic biomass conversion |
| CN103232605A (en) * | 2013-05-21 | 2013-08-07 | 济南圣泉集团股份有限公司 | Hydrogenated phenolic pyrolysis lignin and preparation method thereof |
| CN104177223A (en) * | 2013-05-27 | 2014-12-03 | 天津大学 | Application of transition metal phosphide in catalytic conversion of lignin |
| CN104388110A (en) * | 2014-10-29 | 2015-03-04 | 华东师范大学 | Method for preparing chain alkane from lignin |
Non-Patent Citations (1)
| Title |
|---|
| 孙戈亮: "催化加氢法降解木质素", 《北京工业大学硕士研究生学位论文》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294547A (en) * | 2018-10-23 | 2019-02-01 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of displacement of reservoir oil anionic and nonionic amphoteric surfactant and preparation method thereof |
| CN109294547B (en) * | 2018-10-23 | 2020-11-20 | 天津大港油田滨港集团博弘石油化工有限公司 | Anionic and nonionic amphoteric surfactant for oil displacement and preparation method thereof |
| CN109370633A (en) * | 2018-12-20 | 2019-02-22 | 常州大学 | A kind of lignin adds the method for hydrogen degradation preparation bio oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397495B (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106215951A (en) | A kind of core-shell structure magnetic carbon-based solid acid catalyst and preparation method thereof and the application during lignocellulose hydrolysis and saccharification | |
| CN108355717A (en) | A kind of preparation method of cellulose/BiOBr composite photocatalyst materials | |
| CN110144368B (en) | Method for continuously producing hydrogen after chlorella cell death | |
| CN108671960A (en) | A kind of high hydrothermal stability MOFs catalyst, the method for preparing and preparing chemicals for cellulose conversion | |
| CN101195759B (en) | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst catalysis | |
| CN106397495B (en) | Lignin plus hydrogen catabolite and lignin plus hydrogen biodegrading process | |
| CN103451243A (en) | Method for preparing chemicals from algae through hydrothermal conversion | |
| CN103789365B (en) | Reclaim the method that light oil produces microbial grease | |
| Liu et al. | Producing bioethanol from cellulosic hydrolyzate via co-immobilized cultivation strategy | |
| CN103058852B (en) | Biomass by hydrolyzation prepares the method for lactic acid | |
| CN106475135B (en) | The method of the carbon monoxide-olefin polymeric of co-catalyst and its composition, lignin degrading | |
| CN106905109A (en) | A kind of method that catalytic hydrogenolysis cellulose produces propane diols | |
| CN104014342A (en) | Dual-function magnetic nano solid-base catalyst and preparation method and application thereof | |
| CN102994481A (en) | Preparation method for compound enzyme system for high-efficiency degradation for lignocellulose and application thereof | |
| CN101411985B (en) | Biodiesel composite catalyst and preparation method thereof | |
| CN103668538A (en) | Uvioresistant type biomass polyester fiber and preparation method thereof | |
| CN113289680B (en) | Two-phase catalyst, preparation method thereof and application thereof in lignocellulose biomass conversion | |
| CN106518397A (en) | Method for preparing organic/inorganic mixed activated compound fertilizer from ethyl alcohol filter mud | |
| KR20220094911A (en) | Nanomaterials having cellulase enzyme-mimicking activity and methods of increasing bioethanol production from lignocellulosic biomass using the same | |
| CN103145257B (en) | Water quality stabilizer | |
| CN115259995B (en) | Method for preparing ortho-diol by catalytic hydrogenolysis of lignocellulose | |
| CN110975860A (en) | Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application | |
| CN101085996B (en) | Method for facilitating microbe synthesis of 2,3-butanediol by adding exogenous factor | |
| CN104399515A (en) | High-efficiency composite catalyst for preparing acrylic acid by using lactic acid for catalytic dehydration and preparation method and application of high-efficiency composite catalyst | |
| Sharma et al. | Application of nanomaterials for biofuel production from lignocellulosic biomass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |