WO2018196801A1

WO2018196801A1 - High-concentration biomass slurry and preparation method and use thereof

Info

Publication number: WO2018196801A1
Application number: PCT/CN2018/084589
Authority: WO
Inventors: 郑申棵; 黄⋅J⋅R; 贺蓉; 朱晓玮; 童浩
Original assignee: 武汉凯迪工程技术研究总院有限公司
Priority date: 2017-04-27
Filing date: 2018-04-26
Publication date: 2018-11-01
Also published as: CN106967469B; CN106967469A

Abstract

Disclosed are a high-concentration biomass slurry and a preparation method and the use thereof. The high-concentration biomass slurry is mainly obtained by surface modification of biomass powder particles via an emulsified solution; a swelling effect of the biomass powder particles is effectively inhibited, so that the high-concentration biomass slurry is formed. The method for preparing the high-concentration biomass slurry comprises the following steps: 1) blending a non-polar solvent, an emulsifier and optional water into a stable emulsified solution under the conditions of heating and stirring; and 2) homogeneously mixing pulverized biomass powder particles into the emulsified solution, or adding the emulsified solution during biomass breaking and grinding to make the surfaces of the powder particles be modified. Also disclosed is the use of the high-concentration biomass slurry in fields such as biomass power generation and the preparation of synthetic gas using the biomass. The high-concentration biomass slurry is obtained by modifying the biomass powder particles; and the obtained slurry can be conveyed to downstream working procedures requiring a lower energy consumption by using a slurry pump, and high-pressure stable feeding is realized.

Description

High concentration biomass slurry and preparation method and application thereof

Technical field

The invention relates to a biomass pretreatment technology, in particular to a high concentration biomass slurry and a preparation method and application thereof.

Background technique

Due to the non-renewability of primary energy such as coal, oil and natural gas, and the greenhouse effect and environmental protection problems in use, the clean and environmentally-friendly use of renewable biomass resources with both material and energy properties has shown great potential for development and has become People study and apply the focus of attention.

China's annual output of 700 million tons of agricultural straw and 200 million tons of forestry solid waste, a considerable part of which is abandoned or burned on the spot, resulting in energy waste and environmental pollution. These agro-forest resources biomass can be produced by the gasification reaction after drying and pulverization pretreatment, and the synthesis gas with H ₂ and CO as main components can be generated. This is the main way to realize the clean and environmentally friendly utilization of biomass energy. The purified syngas obtained after gasification can be purified and converted to synthesize clean fuels and high value-added chemicals by Fischer-Tropsch synthesis or other conversion techniques.

Similar to the coal gasification technology, the biomass gasification at this stage mainly uses fuelwood and straw as the main raw materials, and is initially crushed to a suitable particle size range, and is made into a bulk solid (particle size 8 to 50 mm) or solid by inert gas. The particles (particle size 4 to 8 mm) are transported into a gasification furnace for gasification reaction.

High-pressure feed is a prerequisite for high-pressure gasification technology, which can significantly reduce the volume of the gasifier and the energy consumption of the synthesis gas in the downstream section. For solid biomass gasification feedstocks, the pressure of the feed gas in the feed lock hopper is required to be higher than the gasifier pressure to achieve high pressure feed. This feed mode operation is relatively cumbersome and less stable. Due to the use of mechanical valves to seal high-pressure gas, long-term high-frequency switching operations are prone to valve failure or damage, resulting in the gasifier being forced to stop due to feed interruption. At the same time, the inert gas used for the transportation of biomass materials is not easily removed in the downstream section, which will result in a decrease in syngas content and system efficiency. On the other hand, the gasifier requires high stability of the raw materials. Even if the feed amount can be kept stable, the change in the type and composition of the feed biomass will lead to significant changes in gas chemical conditions, gas production and synthesis gas composition. fluctuation. However, the composition of biomass raw materials is complex and varies with the type and season. This poses a challenge to the stable regulation of gasifier conditions and restricts the maturity and improvement of biomass dry gasification technology. Therefore, the high-pressure feed of biomass feedstock and the stability of material composition have become important technical issues affecting its resource utilization.

Similar to the high-pressure feed gasification of coal water slurry, if the biomass raw material is slurried and then fed to the gasifier through the nozzle by the feed pump, the solid feed mode of the biomass can be effectively overcome. Defects, from a technical level, solve the problem of high-pressure stable feed that has long been plagued by biomass gasification technology. At the same time, the biomass slurry can be adjusted in a wide range according to changes in the composition of the raw materials to maintain the stability of the composition of the vaporized material.

The technology for slurry processing of biomass has been widely used in industry, such as the biomass pulping and papermaking and cellulosic ethanol industries. However, due to the swelling effect of the biomass particles after water contact, the slurry concentration (mass percentage content of the biomass component in the slurry) which can be achieved by the conventional method is low, only below 10 wt%, and the calorific value is only 300 kcal. / kg or so, not suitable as a gasification raw material. If the concentration of the biomass slurry is continuously increased, the fluidity will be lost due to the sharp increase in apparent viscosity, resulting in difficulty in feeding or clogging.

Summary of the invention

The object of the present invention is to provide a high-concentration biomass slurry which has high calorific value, good fluidity and can be transported by pump, and a preparation method and application thereof.

In order to achieve the above object, the high-concentration biomass slurry provided by the invention is mainly prepared by surface modification of the biomass powder by the emulsification solution, and the swelling effect of the biomass powder is effectively suppressed to form a high-concentration biomass slurry. material. The emulsified solution is prepared by emulsifier and non-polar solvent, or emulsifier, non-polar solvent and water, and may be O/W type (aqueous phase wrapped oil phase) or W/O type (oil phase wrapped water) Phase) emulsified solution. Biomass is mainly used for fuel crops, crop straws and forestry wastes. It can be directly used to prepare biomass slurry without baking, carbonization or pyrolysis. Of course, the raw materials processed above can also be used for pulping. The non-polar solvent can be selected from the synthetic oil plant waste oil wax; the water can be selected from the process wastewater of the biomass gasification process, which is beneficial to the comprehensive utilization of the synthetic oil plant waste.

Preferably, the mass percentage of each component in the biomass slurry is as follows:

Preferably, the mass fraction of the biomass component in the biomass slurry is not less than 40%, the calorific value is not less than 2500 kcal/kg, and the apparent viscosity is not more than 1500 mPa/s.

Preferably, in the biomass slurry, the mass of the solid particles having a particle diameter of 0.8 mm or more accounts for no more than 1% by weight of the dry material in the slurry (referred to as P _d, +0.8 _mm ≤ 1 wt%).

Preferably, the biomass powder particles have a particle density ranging from 0.7 to 1.4 g/cm ³ , and the particles having a particle diameter of 0.8 mm or more account for no more than 1% by weight of the biomass particles (ie, P _{d, +0.8 mm).} ≤ 1 wt%), high particle density is advantageous for obtaining a higher slurry concentration, and small particle size is advantageous for improving the stability of the biomass slurry.

Preferably, the biomass slurry is further added with an additive, wherein the additive is a surfactant and/or a high molecular polymer, wherein the surfactant may be an ionic, nonionic surfactant or a compound surface. The active agent is preferably an alkyl sulfonate or a lignosulfonate; and the high molecular polymer is a stabilizer for the biomass slurry, preferably a polyethylene oxide or a polystyrene sulfonate. The total mass percentage of the additive in the biomass slurry is from 0.4% by weight to 2% by weight.

Optionally, an optional ingredient is added to the biomass slurry, the optional ingredient being a carbon-containing solid waste and/or a carbon-containing slurry waste, the optional ingredient being in the biomass slurry. The total mass percentage is 0 to 10% by weight. The carbonaceous solid waste is preferably one or more of municipal solid waste, food waste, plastic and waste tire rubber powder, and the carbonaceous slurry waste is preferably organic sludge and/or papermaking black liquor.

Preferably, the non-polar solvent is one or more of oil, grease and wax, and its composition is mainly composed of an alkane, an olefin, an aromatic hydrocarbon or a fat.

Preferably, the emulsifier is one or more of the following anionic/nonionic compounding emulsifiers: 1) alkylphenol ethoxylate (OP-10) and sorbitan monooleate a compound emulsifier of oxyethylene ether (Tween-80), 2) a compound emulsifier of alkylphenol ethoxylate and oleic acid triethanolamine, 3) glyceryl monostearate and sorbitan monooleate a compound emulsifier for ester polyoxyethylene ether, 4) a compound emulsifier of alkyl phenol with ethylene vinyl ether (APEO) and fatty alcohol polyoxyethylene ether (AEO).

Preferably, the emulsifier has a hydrophilic-lipophilic balance in the range of 8-11.

The invention also provides a preparation method of the foregoing high-concentration biomass slurry, comprising the following steps:

1) blending a non-polar solvent, water and an emulsifier, or a non-polar solvent and an emulsifier into a stable emulsified solution under heating and stirring;

2) mixing the pulverized biomass powder and the emulsified solution uniformly, or adding an emulsified solution during the biomass crushing process to modify the surface of the biomass powder.

Preferably, the method further comprises the steps of: 3) blending an additive and/or an optional ingredient in the biomass slurry, the additive being a surfactant and/or a high molecular polymer, the optional ingredients being Carbon solid waste or carbonaceous slurry waste.

Preferably, in the step 1), when the emulsified solution is prepared, the heating temperature is controlled at 50 to 80 ° C, more preferably 70 to 80 ° C; the stirring speed is controlled at 800 to 1200 r / min, and more preferably 950 to 1050 r / min.

The invention also provides several applications of the aforementioned high concentration biomass slurry:

1) The use of the high concentration biomass slurry in boiler fuel is preferably delivered to a biomass power generation boiler by a slurry pump.

2) The use of the high-concentration biomass slurry in biomass gasification to produce syngas is preferably delivered to the biomass gasifier by a slurry pump. By using the high-concentration biomass slurry as a gasification raw material, the high-pressure stable feed of the gasification furnace and the stable output of the synthesis gas can be realized with lower energy consumption.

3) The high-concentration biomass slurry is used for biomass refining to produce high value-added products of cellulose, lignin, nanocellulose, mixed sugars (xylose, arabinose, glucose, mannose and rhamnose), Furfural or small molecule organic acid.

4) The use of the high-concentration biomass slurry in the production of high value-added chemical ethanol.

The biomass slurry is used as a high-concentration raw material for biomass refining or cellulosic ethanol, which is advantageous for increasing product concentration and reducing process energy consumption.

The beneficial effects of the invention are:

1) using an emulsified solution to modify the surface of the biomass powder to effectively inhibit the swelling effect, thereby preparing a high concentration biomass slurry;

2) The biomass can be directly pulverized to obtain a high-concentration biomass slurry having a sufficient heating value and pumpable, thereby realizing energy-saving clean and environmentally-friendly utilization of biomass;

3) In the pulping process, it can make full use of waste oil wax, low-value naphtha and waste washing water and urban energy waste in synthetic oil plants, significantly reduce the investment in downstream pressure-lifting equipment and realize energy saving and consumption reduction of synthetic oil plants. Improve the overall operational efficiency and economic benefits of synthetic oil plants;

4) Applying the high-concentration biomass slurry as a raw material, it can be used as a pumpable gasification raw material of the gasification furnace to achieve low-energy high-pressure stable feed, or as a high-concentration raw material for biomass refining or cellulose ethanol. Conducive to increase product concentration and reduce process energy consumption.

DRAWINGS

1 is a schematic view showing a process flow for preparing a high-concentration biomass slurry provided by the present invention.

2 is a schematic view showing a process flow of a high-concentration biomass slurry provided by the present invention applied to a biomass boiler.

FIG. 3 is a schematic diagram of a process flow of a high-concentration biomass slurry provided by the present invention applied to biomass synthesis gas.

4 is a schematic diagram of a process flow of a high-concentration biomass slurry provided for biomass refining provided by the present invention.

FIG. 5 is a schematic view showing the process flow of the high-concentration biomass slurry provided by the present invention for producing cellulosic ethanol.

detailed description

The invention will be further described in detail below with reference to the drawings and specific embodiments.

Example 1

The high-concentration biomass slurry provided in this embodiment has the following composition and preparation method:

1) 100kg Fischer-Tropsch synthesis of aqueous phase product (main component is water, containing a small amount of water, alcohol, aldehyde, acid and other organic matter), 15kg of waste engine oil, and 3kg of OP-10 and Tween-80 compound emulsifier (Hydrophilic lipophilic balance value of 9.0) mixed to form an emulsified solution, the heating temperature is controlled at 75 ° C, the stirring speed is controlled at 1000 r / min;

2) mixing the granules obtained by pulverizing 270 kg of shaped biomass pellets (particle density of 1.4 g/cm ³ ) with 118 kg of the emulsified solution obtained in the step 1);

3) 1.5 kg of alkyl sulfonate and 0.5 kg of polyethylene oxide (additive) were added and stirred to form a high concentration biomass slurry.

Example 2

1) Mixing 240kg of syngas purification and washing waste water, 20kg of dining waste oil, and 4kg of OP-10 and oleic acid triethanolamine compound emulsifier (hydrophilic-lipophilic balance value of 9.7) to prepare emulsified solution, heating temperature Control at 80 ° C, the stirring speed is controlled at 1100r / min;

2) 200 kg of wheat straw granules (particle density after compression is 0.7 g/cm ³ ) is ground and refined in a 3-stage tandem double-disc mill, and 264 kg of the emulsified solution obtained in step 1) is added during the refining process;

3) Adding 2 kg of lignosulfonate (additive) and 20 kg of dried municipal sludge (optional ingredient) having a solid content of 80% by weight to form a high-concentration biomass slurry.

Example 3

1) Mix 250kg of naphtha with 2kg of glyceryl monostearate/Tween-20 (hydrophilic-lipophilic balance value of 8.1) to prepare an emulsified solution, the heating temperature is controlled at 70 ° C, stirring speed Control at 900r/min;

2) 180kg of twig smashed wood chips (particle density of 0.9g/cm ³ ) was mixed with 252kg of emulsified solution obtained in step 1);

3) Add 1.8 kg of alkyl sulfonate and 0.2 kg of polystyrene sulfonate (additive) and 10 kg of papermaking black liquor (optional formulation) having a solid content of 60% by weight, and stir to form a high concentration biomass slurry.

Example 4

1) Mix 80kg process wastewater, 80kg crude benzene solution, and 8kg OP-10 with Tween-80 compound emulsifier (hydrophilic-lipophilic balance value 9.0) to prepare an emulsified solution. The heating temperature is controlled at 50 °C. , the stirring speed is controlled at 800r/min;

2) 200 kg of chaff and rice straw were subjected to steam explosion treatment and further pulverized (average particle density was 0.8 g/cm ³ ), and the mixed powder was mixed with 168 kg of the emulsified solution obtained in the step 1);

3) Add 8 kg of alkyl sulfonate (additive) and 40 kg of waste tire rubber powder (optional ingredients) and stir to form a high concentration biomass slurry.

Example 5

1) Mix 80 kg of water, 35 kg of paraffin wax, and 5 kg of alkylphenol with a compound emulsifier of epoxy vinyl ether (APEO) and fatty alcohol polyoxyethylene ether (AEO) (hydrophilic-lipophilic balance value of 10.8) It is formulated into an emulsified solution, the heating temperature is controlled at 85 ° C, and the stirring speed is controlled at 1000 r / min. ;

2) mixing powder of 200 kg of wood chips and medium-density board waste material (average particle density of 1.1 g/cm ³ ), and mixing with 120 kg of the emulsified solution obtained in step 1);

3) After adding 4 kg of polystyrene sulfonate (additive), it is stirred to form a high concentration biomass slurry.

The process flow for preparing high-concentration biomass slurry in the above Examples 1 to 5 is shown in Fig. 1, and the dotted line in the figure is an alternative process route.

The mass percentages of the high-concentration biomass slurry obtained in the above Examples 1 to 5 are listed in Table 1. The results of the physical and chemical properties are listed in Table 2. The comparison sample in Table 2 is the detection of the pumpable biomass slurry in the pulp and paper workshop. result. As can be seen from Table 2, compared with the papermaking biomass slurry, the present invention substantially increases the mass percentage content of the biomass component and the slurry calorific value in the biomass slurry without significantly increasing the apparent viscosity of the slurry. The slurry is allowed to stand for 24 hours without delamination and has good stability.

Table 1 The mass percentage content of each component in the slurry obtained in Examples 1-5

浆料组成Slurry composition	实施例1Example 1	实施例2Example 2	实施例3Example 3	实施例4Example 4	实施例5Example 5
生物质粉粒Biomass powder	69.23％69.23%	41.15％41.15%	40.54％40.54%	48.08％48.08%	61.73％61.73%
水water	25.64％25.64%	49.38％49.38%	00	19.23％19.23%	24.69％24.69%
非极性溶剂Non-polar solvent	3.85％3.85%	4.12％4.12%	56.31％56.31%	19.23％19.23%	10.80％10.80%
乳化剂Emulsifier	0.77％0.77%	0.82％0.82%	0.45％0.45%	1.92％1.92%	1.54％1.54%
添加剂additive	0.51％0.51%	0.41％0.41%	0.45％0.45%	1.92％1.92%	1.23％1.23%
可选配料Optional ingredients	00	4.12％4.12%	2.25％2.25%	9.62％9.62%	00

Table 2 Comparison of the properties of the slurry obtained in Examples 1-5 with conventional pumpable pulp

Example 6

The above-mentioned high-concentration biomass slurry is used as a fuel for a biomass power generation boiler, and the process flow thereof is as shown in FIG. 2 . The high-concentration biomass slurry stored in the slurry storage tank is sent to the combustion chamber of the boiler through the feed pump to generate heat in the air atmosphere to provide energy for the boiler circulating medium (usually water), and the combustion exhaust gas is separated by the dust removal system. The solid particles in the gas are discharged.

Example 7

The above-mentioned high-concentration biomass slurry is used as a raw material for gasification of biomass to produce synthesis gas, and the process flow thereof is shown in FIG. The high-concentration biomass slurry stored in the slurry storage tank is sent to the nozzle of the entrained flow gasification furnace through a pressurized feed pump, and gasification reaction is carried out in a gas or oxygen atmosphere in the gasification chamber, and the obtained synthesis gas is subjected to dust removal and decoking. It is used in downstream chemical synthesis processes after treatment.

Example 8

The above-mentioned high-concentration biomass slurry is used as a raw material for biomass refining, and the process flow thereof is shown in FIG. 4 . The high concentration biomass slurry is pretreated by acid hydrolysis or high temperature hydrolysis to separate the main components of lignin, cellulose and hemicellulose. These components can be used as a platform material for biomass refining for subsequent target product conversion. For example, the cellulose can be homogenized by a homogenizer, and the nanocellulose is separated by the TEMPO oxidation method commonly used in the industry. Hemicellulose can be subjected to saccharification hydrolysis to obtain mixed sugars (xylose, arabinose, glucose, mannose, and rhamnose), furfural, and small molecule organic acids.

Example 9

The aforementioned biomass slurry is used as a high-concentration raw material for cellulosic ethanol production, and the process flow thereof is shown in FIG. 5. The cellulose obtained by hydrolysis or acid hydrolysis of the high-concentration biomass slurry is subjected to saccharification and hydrolysis to obtain a mixed sugar liquid containing glucose as an important component, and then fermented to obtain a fermentation liquid containing an ethanol product, which is further separated by distillation to obtain a target product ethanol.

Claims

A high-concentration biomass slurry characterized in that: the biomass powder is mainly obtained by surface modification of an emulsified solution; the emulsified solution is composed of an emulsifier and a non-polar solvent, or an emulsifier, a non-polar solvent, and Water is prepared.
The high-concentration biomass slurry according to claim 1, wherein the mass percentage of each component in the biomass slurry is as follows:
The high-concentration biomass slurry according to claim 1, wherein the biomass slurry has a calorific value of not less than 2500 kcal/kg and an apparent viscosity of not more than 1500 mPa/s.
The high-concentration biomass slurry according to any one of claims 1 to 3, wherein in the biomass slurry, the material having a solid particle diameter of 0.8 mm or more accounts for the mass percentage of the dry material in the slurry. Not more than 1% by weight.
The high-concentration biomass slurry according to any one of claims 1 to 3, wherein the biomass powder particles have a particle density in the range of 0.7 to 1.4 g/cm 3 .
The high-concentration biomass slurry according to any one of claims 1 to 3, wherein an additive is added to the biomass slurry, and the additive is a surfactant and/or a polymer. The total mass percentage of the additive in the biomass slurry is from 0.4% by weight to 2% by weight.
The high-concentration biomass slurry according to claim 6, wherein the surfactant is an alkyl sulfonate or a lignosulfonate, and the polymer is polyethylene oxide or polyphenylene. Ethylene sulfonate.
The high-concentration biomass slurry according to any one of claims 1 to 3, characterized in that the biomass slurry is further provided with an optional ingredient, which is a carbon-containing solid waste and/or Or carbonaceous slurry waste, the total mass percentage of the optional ingredients in the biomass slurry being from 0 to 10% by weight.
The high-concentration biomass slurry according to claim 8, wherein the carbon-containing solid waste is one or more of urban solid waste, food waste, plastic and waste tire rubber powder, The slurry waste of carbon is organic sludge and/or papermaking black liquor.
The high-concentration biomass slurry according to any one of claims 1 to 3, wherein the non-polar solvent is one or more of oil, grease and wax.
The high-concentration biomass slurry according to any one of claims 1 to 3, wherein the emulsifier is one or more of the following complex emulsifiers: 1) alkylphenol polyoxygen a compound emulsifier of vinyl ether and sorbitan monooleate polyoxyethylene ether, 2) a compound emulsifier of alkylphenol ethoxylate and oleic acid triethanolamine, 3) glyceryl monostearate a complex emulsifier of sorbitan monooleate polyoxyethylene ether, 4) a compound emulsifier of alkyl phenol with ethylene vinyl ether and fatty alcohol polyoxyethylene ether.
The high-concentration biomass slurry according to any one of claims 1 to 3, wherein the emulsifier has a hydrophilic-lipophilic balance value in the range of 8 to 11.
A method for preparing a high-concentration biomass slurry according to any one of claims 1 to 12, comprising the steps of:

1) blending a non-polar solvent, water and an emulsifier, or a non-polar solvent and an emulsifier into a stable emulsified solution under heating and stirring;

2) mixing the pulverized biomass powder with the emulsified solution, or adding an emulsification solution during the biomass crushing process to modify the surface of the biomass powder.
The method for preparing a high-concentration biomass slurry according to claim 13, characterized in that the method further comprises the steps of: 3) blending an additive and/or an optional ingredient in the biomass slurry, the additive being A surfactant and/or a high molecular polymer, the optional ingredient being a carbonaceous solid waste or slurry waste.
The method for preparing a high-concentration biomass slurry according to claim 13 or 14, wherein in the step 1), when the emulsified solution is prepared, the heating temperature is controlled at 50 to 80 ° C, and the stirring speed is controlled at 800 to 1200 r / Min.
The method for preparing a high-concentration biomass slurry according to claim 13 or 14, wherein in the step 1), when the emulsified solution is prepared, the heating temperature is controlled at 70 to 80 ° C, and the stirring speed is controlled at 950 to 1050 r / Min.
Use of a high concentration biomass slurry according to any one of claims 1 to 12 in boiler fuel.
Use of a high concentration biomass slurry according to any one of claims 1 to 12 for biomass gasification to produce synthesis gas.
Use of the high-concentration biomass slurry according to any one of claims 1 to 12 for producing high value-added products of cellulose, lignin, nanocellulose, mixed sugar, furfural or small molecule organic acid.
Use of a high concentration biomass slurry according to any one of claims 1 to 12 for the production of high value-added chemical ethanol.