CN115434178B - Chemical alkali recovery treatment process for chemical mechanical pulp waste liquid - Google Patents
Chemical alkali recovery treatment process for chemical mechanical pulp waste liquid Download PDFInfo
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- CN115434178B CN115434178B CN202211017370.7A CN202211017370A CN115434178B CN 115434178 B CN115434178 B CN 115434178B CN 202211017370 A CN202211017370 A CN 202211017370A CN 115434178 B CN115434178 B CN 115434178B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5209—Regulation methods for flocculation or precipitation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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Abstract
The application discloses a chemical alkali recovery treatment process of chemical machine pulp waste liquid, which comprises the following steps: adding a pretreatment reagent into the chemical mechanical pulp waste liquid to perform pretreatment reaction, and obtaining a first mixture system after the pretreatment reaction is completed; the pretreatment reagent is at least one of a hydrophobic modifier, a free radical reaction initiator and a metal ion salting-out agent; the pH value of the chemical mechanical pulp waste liquid is 12-14; adding a flocculating agent into the first mixture system to carry out precipitation reaction, and obtaining a second mixture system after the precipitation reaction is completed; carrying out solid-liquid separation on the second mixture system to obtain solid organic sediment and alkaline recovery liquid; the pH of the alkaline recovery solution is 11.8-13. The treatment process disclosed by the application is simple in process, low in energy consumption, capable of efficiently recycling the organic matters and alkali liquor in the chemical mechanical pulp waste liquid, high in economic value and suitable for popularization and application in industry.
Description
Technical Field
The application belongs to the technical field of pulping waste liquid recovery treatment, and particularly relates to a chemical alkali recovery treatment process of chemical pulping waste liquid.
Background
At present, along with the promotion of waste limiting, the imported waste paper quantity is continuously reduced, the problem of raw material supply shortage in the domestic papermaking industry is increasingly serious, some paper-making enterprises with higher imported waste paper raw material dependency are sequentially erected to construct a large-scale natural-color machine pulp production line with thousands of tons of daily products, small and medium-sized enterprises in other places are actively invested according to local conditions, the new machine pulp production line is not equal from 300t of daily products to 600t/d of medium scale in the entrance level, and the domestic machine pulp production and technical market initially present an industry new pattern of multi-level production scale and diversified technical routes.
In the newly-increased capacity of the machine pulp, besides the modern machine pulp production processes such as classical ATMP, CTMP, APMP and the like, a considerable part of enterprises select cold alkalization machine pulp production technologies with small investment, short construction period and simple process according to market demand conditions, and the method is mainly applied to the construction of production lines with the scale of about 10 ten thousand tons/year.
Cold alkalization machine pulp production technology is originally found in the patent issued by Australian Woodhead in 1934, and uses caustic soda solution at normal temperature and normal pressure to impregnate raw materials of wood chips such as eucalyptus and the like, and then fluffs the softened wood chips to obtain pulp. In 1960, the research works of Sloman and Torner et al show that the cold alkalizing machine pulp process is particularly suitable for the production of hardwood raw materials, has the unique technical advantages of simple and easily obtained pulping chemicals, high pulping yield (generally 80% -85%), extremely low fiber bundle content, few fiber cutting and the like, and can reach the whiteness of pulp of more than 72% GE after simple bleaching, thereby meeting the production requirements of common cultural paper.
The method is characterized in that a cold alkalizing machine pulp technology is utilized to treat corrugated boards made of forest small-size materials in the early 60 th century, a caustic soda solution with the concentration of 31.4g/L is utilized, and the method comprises the following steps: 9 liquid ratio, 2h dipping treatment is carried out on wood chips of small-specification wood materials in forest areas such as pine, poplar and the like, and corrugated base paper products with longitudinal fracture length of more than 5km can be manufactured after disc grinding, pulping and washing treatment, the pulping yield reaches more than 85%, and the production quality requirement of the products is well met. The main technical advantages are strong adaptability of raw materials, high pulping yield, high strength and low pulping energy consumption; the main disadvantage is that the pulping waste liquid is large in generation amount (basically equivalent to the generation amount of chemical pulp black liquor); the concentration of residual alkali in the waste liquid is about 3 percent, which is far higher than that of the alkali chemical pulp black liquor, but the concentration of organic matters is lower, which is about 2.5 percent of the total amount of the waste liquid, and the combustion heat value is low, so that the evaporation, concentration and combustion cannot be carried out by utilizing the classical modern alkali recovery technology, thereby realizing the self-supply of energy.
The main difficulty in realizing caustic soda recovery in cold alkalizing machine slurry waste liquid is as follows: in order to maintain a high caustic soda recovery rate to meet the recycling requirement of cold alkalization machine pulp and reduce the operation cost of chemical alkali recovery, all chemical reactions and chemical separation processes need to be completed in an alkaline environment (typically, the pH=12-14 of the cold alkalization machine pulp waste liquid). Therefore, the conventional polysaccharide separation and sedimentation techniques such as acid precipitation and alcohol precipitation are carried out by using dilute acid or by passing throughInto high temperature flue gas (typically CO 2 、SO 2 Etc.), the pH value of the system is reduced, and although the hemicellulose sedimentation separation can be realized, caustic soda loss is necessarily caused in the implementation process, and the technical target requirements of caustic soda recovery and recycling cannot be met. Therefore, the unique early-stage slurry production technology is gradually replaced by modern slurry production technologies such as PRC APMP, BCTMP and the like with larger regulation, smaller wastewater generation amount and smaller pollution load in recent decades due to the problem of environmental pollution which is difficult to solve.
Under the current situation, the research on cold alkalization machine pulp waste liquid treatment technology is actively developed, the comprehensive utilization problem of caustic soda recovery and alkali dissolution components of plant fiber raw materials such as wood is developed, the potential application value of the traditional technology is developed, the effective way of recycling forest processing leftovers such as branch materials and various straw agricultural waste raw materials widely existing in mountain forest areas and agricultural reclamation areas in China is realized, and the method plays an important role in relieving the problem of raw material shortage in the papermaking industry in China.
Disclosure of Invention
Based on the background, the application develops a chemical alkali recovery treatment technology by utilizing the hydrophobic modification reaction, salting-out and sedimentation separation action mechanism of polysaccharide compounds such as hemicellulose and the like under the high pH value reaction condition aiming at the composition characteristics of high residual alkali and low organic matter content in the cold alkalization machine pulp waste liquid, promotes the polysaccharide organic matters such as hemicellulose and the like after the hydrophobic modification or salting-out damage colloid hydration layer in the cold alkalization machine pulp waste liquid to lose alkali solubility and quickly gather and sediment, completes the separation and purification of the cold alkalization machine pulp waste liquid, obtains regenerated caustic soda solution which can be circularly applied to the production of the cold alkalization machine pulp, simultaneously obtains polysaccharide byproducts such as hemicellulose and the like with comprehensive utilization value, realizes the technical aim of full component recovery and cyclic utilization of the cold alkalization machine pulp waste liquid, and thoroughly solves the environmental pollution problem caused by the production of the cold alkalization machine pulp.
In order to achieve the aim of the application, the application provides a chemical alkali recovery treatment process for chemical pulp waste liquid, which comprises the following steps:
adding a pretreatment reagent into the chemical mechanical pulp waste liquid to perform pretreatment reaction, and obtaining a first mixture system after the pretreatment reaction is completed; the organic matter settling agent is at least one of a hydrophobic modifier, a free radical reaction initiator and a metal ion salting-out agent; the pH value of the chemical mechanical pulp waste liquid is 12-14;
adding a flocculating agent into the first mixture system to carry out a precipitation reaction, and obtaining a second mixture system after the precipitation reaction is completed;
carrying out solid-liquid separation on the second mixture system to obtain solid organic sediment and alkaline recovery liquid; the pH value of the alkaline recovery liquid is 11.8-13.
Further, the hydrophobic modifier is at least one of a silane coupling agent, 1, 2-alkylene oxide and alkenyl succinic anhydride.
Further, the silane coupling agent is at least one of gamma-chloropropyl triethoxysilane, gamma-chloropropyl methyl dichlorosilane, gamma-chloropropyl trimethoxysilane, gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane.
Further, the free radical reaction initiator is at least one of persulfate, azo compound and hydroperoxide.
Further, the persulfate is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
Further, the metal ion salting-out agent is at least one of sodium chloride, potassium chloride and lithium chloride.
Further, the flocculant is at least one of polyaluminum chloride, anionic polyacrylamide and ferric trichloride.
Further, the addition amount of the hydrophobic modifier is 10-20 g/L; and/or
The addition amount of the free radical reaction initiator is 5-15 g/L; and/or
The adding amount of the metal ion salting-out agent is 5-15 g/L.
Further, the addition amount of the flocculant is 0.1-0.4 g/L.
Further, the temperature of the pretreatment reaction is 30-90 ℃ and the time is 30-90 min.
Compared with the prior art, the application has the following technical effects:
according to the chemical alkali recovery treatment process for the chemical mechanical pulp waste liquid, most of organic matters in the chemical mechanical pulp waste liquid can be efficiently precipitated after the pretreatment reagent and the flocculating agent are added into the chemical mechanical pulp waste liquid, and the precipitated solid organic sediment can be directly recovered and reused, so that the utilization efficiency of the organic matters in the chemical mechanical pulp waste liquid is improved; in addition, after the treatment process provided by the application, the alkaline recovery liquid can still maintain a higher pH level, so that the alkaline recovery liquid can be directly recovered and recycled to be used as the alkaline leaching liquid of the cold alkali process papermaking wood pulp, and the consumption of neoalkali is reduced.
The chemical alkali recovery treatment process of the chemical mechanical pulp waste liquid has simple process and low energy consumption, can efficiently recover organic matters and alkali liquor in the chemical mechanical pulp waste liquid, has higher economic value, and is suitable for industrial popularization and application.
According to the chemical alkali recovery treatment process of the chemical pulp waste liquid, a polysaccharide compound efficient hydrophobic modification reaction and/or salting-out-sedimentation separation system under an overbased environment is constructed, so that a purified regenerated caustic soda solution and hemicellulose polysaccharide byproducts which can be used for subsequent processing are synchronously obtained.
The implementation of the chemical alkali recovery technology route provided by the chemical alkali recovery treatment process of the chemical machine pulp waste liquid has positive practical significance for solving the serious environmental pollution problem generated by the cold alkalization machine pulp process, activating the inherent technical advantages thereof and helping the pulping and papermaking industry of China to get rid of the raw material shortage dilemma as early as possible; the method plays an important role in further enriching the technical means of alkali recovery and comprehensive utilization of the alkali process chemical pulp black liquor, promoting the pulping and papermaking industry to realize zero discharge of waste liquor, promoting low-carbon development of the industry and realizing long-term green manufacturing targets.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The embodiment of the application provides a chemical alkali recovery treatment process for chemical mechanical pulp waste liquid, which comprises the following steps:
(1) Adding a pretreatment reagent into the chemical mechanical pulp waste liquid to perform pretreatment reaction, and obtaining a first mixture system after the pretreatment reaction is completed; the pretreatment reagent is at least one of a hydrophobic modifier, a free radical reaction initiator and a metal ion salting-out agent; the pH value of the chemical mechanical pulp waste liquid is 13-14;
(2) Adding a flocculating agent into the first mixture system to carry out precipitation reaction, and obtaining a second mixture system after the precipitation reaction is completed;
(3) Carrying out solid-liquid separation on the second mixture system to obtain solid organic sediment and alkaline recovery liquid; the pH of the alkaline recovery solution is 11.8-13.
The chemical mechanical pulp waste liquid of the embodiment of the application is from waste liquid produced by a chemical mechanical pulp papermaking process, in particular to waste liquid obtained by cold alkali dipping poplar chips, wherein the cold alkali dipping temperature is 50 ℃, the dipping time is 4 hours, and the alkali mass concentration is 4%. The chemical mechanical pulp waste liquid in the embodiment of the application comprises the following components in parts by weight: organic matters such as xylose (30% -60%), lignin (1% -10%), uronic acid arabinose (0% -2%), glucose (0% -2%), acetic acid (30% -60%), formic acid (0% -2%), and the like, and the pH of the alkali impregnation waste liquid is 13-14. The mass concentration of the organic matters in the waste liquid is 1-100 g/L.
In the step (1), after the hydrophobic modifier is added into the chemical mechanical pulp waste liquid, the hydrophobic modifier can carry out hydrophobic modification on the organic matters in the waste liquid, so that the compatibility and the dispersibility of the modified organic matters in the waste liquid are weakened, and the organic matters after the hydrophobic modification are more easily precipitated from a waste liquid system. In the embodiment of the application, the hydrophobic modifier can be at least one of silane coupling agent, 1, 2-alkylene oxide and alkenyl succinic anhydride. Specifically, the silane coupling agent can be at least one of gamma-chloropropyl triethoxysilane, gamma-chloropropyl methyl dichlorosilane, gamma-chloropropyl trimethoxysilane, gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane.
In the specific embodiment of the application, a silane coupling agent is used as a hydrophobic modifier of an organic matter. The addition amount of the hydrophobic modifier is 10-20 g/L, namely 10-20 g, preferably 15g/L, of the hydrophobic modifier is added into each liter of waste liquid. After the silane coupling agent is added, alkoxy- (OR) in the silane coupling agent is reacted in the pretreatment process 3 Firstly, the coupling agent molecules react with water in the waste liquid or water on the surface of organic matters containing hydroxyl groups to generate silicon hydroxyl groups (SiOH-), then, the coupling agent molecules generate siloxane Si-O-Si with lower polymerization degree through partial dehydration condensation reaction among the silicon hydroxyl groups, meanwhile, the silicon hydroxyl groups still have abundant silicon hydroxyl SiOH-, on the structure, form hydrogen bond action with the hydroxyl groups on the surface of the organic matters, and then, the hydroxyl groups are further dehydrated to enable the coupling agent molecules to form stable covalent bonds with the surface of the organic matters, so that the organic matters in the waste liquid are divided by the silane coupling agent, one end with the hydroxyl groups is tightly combined with the silane coupling agent, and the other end is keyed with hydrophobic organic groups to change the surface properties of the organic matters particles, so that the surface energy is reduced, the compatibility and the dispersibility of the coupling agent molecules in an aqueous phase system are weakened, and the subsequent flocculation precipitation treatment is facilitated.
In the step (1), a radical reaction initiator may be added to the chemical mechanical pulp waste liquid to precipitate the organic matters in the waste liquid. The free radical reaction initiator can crosslink organic molecules in the waste liquid and convert the organic molecules into macromolecular organic substances with lower water solubility, thereby facilitating subsequent flocculation and precipitation treatment. In the embodiment of the application, the free radical reaction initiator can be at least one selected from persulfates, azo compounds and hydroperoxides. Specifically, the persulfate is taken as an initiator of the free radical reaction, and the persulfate can be at least one of potassium persulfate, sodium persulfate and ammonium persulfate. The amount of the radical initiator to be added is 5 to 15g/L, preferably 8g/L. After persulfate is added into the chemical mechanical pulp waste liquid, the persulfate and the organic matters with hydroxyl groups in the waste liquid are subjected to crosslinking reaction, and free radicals generated by the persulfate can crosslink the organic matters into macromolecular organic matters with lower water solubility.
In the step (1), a metal ion salting-out agent may be added to the chemical mechanical pulp waste liquid to promote sedimentation separation of organic matters in the waste liquid. After the metal ion salting-out agent is added, cations can attract a large amount of free water molecules due to strong hydration in the aqueous solution in the salting-out process due to the salting-out effect of the metal ions, and the concentration of the free water molecules in the aqueous solution of the organic matters is reduced, so that the organic matters in the waste liquid are promoted to flocculate, and the subsequent flocculation precipitation treatment is facilitated. In the embodiment of the application, the metal ion salting-out agent can be at least one of sodium chloride, potassium chloride and lithium chloride. The amount of the metal ion salting-out agent to be added is 5 to 15g/L, preferably 8g/L.
In the step (1), the temperature of the pretreatment reaction can be controlled to be 30-90 ℃ and the time is 30-90 min. Under the condition of the precipitation reaction, organic matters in the waste liquid can be quickly and efficiently precipitated.
In the step (2), the flocculant can be at least one of polyaluminum chloride, anionic polyacrylamide and ferric trichloride. Flocculating suspended particles in the waste liquid by adding a flocculating agent to the first mixture system pretreated in the step (1) so as to promote the suspended particles to quickly settle from the waste liquid. The addition amount of the flocculant is selected to be 0.1-0.4 g/L, preferably 0.25g/L. The precipitation reaction can be carried out at room temperature, and the time of the precipitation reaction can be regulated and controlled according to the content of organic matters in the waste liquid.
In the step (3), after solid-liquid separation, the solid organic sediment (comprising about 95% hemicellulose and about 5% lignin) can be directly recycled as a high added value product, and can be used as a packaging material, a papermaking additive, a decorative coating, and in foods or biological medicines; the pH value of the alkaline recovery liquid is 11.8-13, namely, the concentration of alkali in the alkaline recovery liquid is reduced to a small extent, and the higher pH value level is still maintained, so that the alkaline recovery liquid can be directly recovered and recycled to be used as the alkaline leaching liquid of the cold alkali process papermaking wood pulp, and the consumption of neoalkali is reduced. The alkali in the alkaline recovery liquid in the embodiment of the application can be sodium hydroxide or potassium hydroxide.
According to the chemical alkali recovery treatment process for the chemimechanical pulp waste liquid, the pretreatment reagent is added into the chemimechanical pulp waste liquid to improve the sedimentation performance of organic matters in the waste liquid, and then the flocculating agent is added to promote flocculation sedimentation of the organic matters, so that most of the organic matters in the chemimechanical pulp waste liquid can be efficiently precipitated, the precipitated solid organic sediment can be directly recovered and reused, and the utilization efficiency of the organic matters in the chemimechanical pulp waste liquid is improved; in addition, after the treatment process of the embodiment of the application is carried out, the alkaline recovery liquid can still maintain a higher pH level, so that the alkaline recovery liquid can be directly recovered and recycled to be used as the alkaline leaching liquid of the papermaking wood pulp of the cold alkaline process, the consumption of new alkali is reduced, the problems of alkali loss, organic matters waste and the like in the traditional alkali recovery are overcome, the effect of separating the alkali solution is achieved through the sedimentation of the organic matters, and the cost and the environmental risk of alkali recovery are reduced.
The chemical alkali recovery treatment process of the chemical mechanical pulp waste liquid is simple in process, low in energy consumption, capable of efficiently recovering organic matters and alkali liquor in the chemical mechanical pulp waste liquid, high in economic value and suitable for industrial popularization and application.
According to the chemical alkali recovery treatment process of the chemical mechanical pulp waste liquid, the polysaccharide compound efficient hydrophobic modification reaction and/or salting-out-sedimentation separation system under the high alkaline environment is constructed, so that the purified regenerated caustic soda solution and hemicellulose polysaccharide byproducts which can be used for subsequent processing are synchronously obtained.
The implementation of the chemical alkali recovery technology route provided by the chemical alkali recovery treatment process of the chemimechanical pulp waste liquid has positive practical significance for solving the serious environmental pollution problem generated by the cold alkalization pulping process, activating the inherent technical advantages thereof and helping the pulping and papermaking industry of China get rid of the raw material shortage dilemma as soon as possible; the method plays an important role in further enriching the technical means of alkali recovery and comprehensive utilization of the alkali process chemical pulp black liquor, promoting the pulping and papermaking industry to realize zero discharge of waste liquor, promoting low-carbon development of the industry and realizing long-term green manufacturing targets.
The chemical alkali recovery treatment process of the chemical pulp waste liquid according to the embodiment of the application is exemplified by a plurality of specific embodiments.
Example 1
The embodiment 1 of the application provides a chemical alkali recovery treatment process for chemical pulp waste liquid, which comprises the following steps:
(1) Adding 10g of gamma-chloropropyl triethoxysilane into 5L of alkali impregnation waste liquid to obtain a mixed solution A;
(2) Stirring the mixed solution A obtained in the step (1) at 35 ℃ for reaction for 60min;
(3) And (3) dropwise adding 100mL of 0.1g/mL polyaluminium chloride into the mixture system obtained in the step (2) under the stirring condition, wherein the stirring speed is 2000-4000 rpm, and the stirring speed is 200-500 rpm after the addition is finished, and carrying out precipitation reaction for 10min.
(4) And (3) carrying out suction filtration on the mixture system obtained in the step (3), and separating solid and liquid to obtain solid organic sediment and alkaline recovery liquid.
The alkali impregnation waste liquid of the example of the present application was subjected to the following table 1 for the content of each main component (the content value of each main component was measured by liquid chromatography) and the pH change before and after the treatment:
TABLE 1
In Table 1, "-" indicates that no corresponding components were detected, and as can be seen from Table 1, the treatment method of example 1 of the present application can precipitate 98% or more of the organic matters in the waste liquid, thereby efficiently separating the organic matters from the waste liquid, and the pH of the waste liquid can be maintained at a high alkaline level before and after separation.
Example 2
The embodiment 2 of the application provides a chemical alkali recovery treatment process for chemical pulp waste liquid, which comprises the following steps:
(1) 50g of potassium persulfate is added into 5L of alkali impregnation waste liquid to obtain a mixed solution A;
(2) Stirring the mixed solution A obtained in the step (1) at 60 ℃ for reaction for 90min;
(3) And (3) dropwise adding 100mL of 0.1g/mL polyaluminium chloride into the mixture system obtained in the step (2) under the stirring condition, wherein the stirring speed is 2000-4000 rpm, and the stirring speed is 200-500 rpm after the addition is finished, and carrying out precipitation reaction for 10min.
(4) And (3) carrying out suction filtration on the mixture system obtained in the step (3), and separating solid and liquid to obtain solid organic sediment and alkaline recovery liquid.
The alkali impregnation waste liquid of the example of the present application was subjected to the following table 2 for the content of each main component (the content value of each main component was measured by liquid chromatography) and the pH change before and after the treatment:
TABLE 2
In Table 2, "-" indicates that no corresponding components were detected, and as can be seen from Table 2, the treatment method of example 2 of the present application can precipitate 98% or more of the organic matters in the waste liquid, thereby efficiently separating the organic matters from the waste liquid, and the pH of the waste liquid can be maintained at a high alkaline level before and after separation.
Example 3
The embodiment 3 of the application provides a chemical alkali recovery treatment process for chemical pulp waste liquid, which comprises the following steps:
(1) Adding 50g of lithium chloride into 5L of alkali impregnation waste liquid to obtain a mixed solution A;
(2) Stirring the mixed solution A obtained in the step (1) at 30 ℃ for reaction for 90min;
(3) And (3) dropwise adding 100mL of 0.1g/mL polyaluminium chloride into the mixture system obtained in the step (2) under the stirring condition, wherein the stirring speed is 2000-4000 rpm, and the stirring speed is 200-500 rpm after the addition is finished, and carrying out precipitation reaction for 10min.
(4) And (3) carrying out suction filtration on the mixture system obtained in the step (3), and separating solid and liquid to obtain solid organic sediment and alkaline recovery liquid.
The alkali impregnation waste liquid of the example of the present application before and after the treatment, wherein the content of each main component (the content value of each main component is measured by liquid chromatography) and the pH change are shown in table 3 below:
TABLE 3 Table 3
In Table 3, "-" indicates that no corresponding components were detected, and as can be seen from Table 3, the treatment method of example 3 of the present application can precipitate 98% or more of the organic matters in the waste liquid, thereby efficiently separating the organic matters from the waste liquid, and the pH of the waste liquid can be maintained at a high alkaline level before and after separation.
Example 4
The embodiment 4 of the application provides a chemical alkali recovery treatment process for chemical pulp waste liquid, which comprises the following steps:
(1) Adding 50g of calcium chloride into 5L of alkali impregnation waste liquid to obtain a mixed solution A;
(2) Stirring the mixed solution A obtained in the step (1) at 30 ℃ for reaction for 90min;
(3) And (3) dropwise adding 100mL of 0.1g/mL polyaluminium chloride into the mixture system obtained in the step (2) under the stirring condition, wherein the stirring speed is 2000-4000 rpm, and the stirring speed is 200-500 rpm after the addition is finished, and carrying out precipitation reaction for 10min.
(4) And (3) carrying out suction filtration on the mixture system obtained in the step (3), and separating solid and liquid to obtain solid organic sediment and alkaline recovery liquid.
The alkali impregnation waste liquid of the example of the present application before and after the treatment, wherein the content of each main component (the content value of each main component is measured by liquid chromatography) and the pH change are shown in the following table 4:
TABLE 4 Table 4
Example 5
The embodiment 5 of the application provides a chemical alkali recovery treatment process for chemical pulp waste liquid, which comprises the following steps:
(1) Adding 50g of sodium chloride into 5L of alkali impregnation waste liquid to obtain a mixed solution A;
(2) Stirring the mixed solution A obtained in the step (1) at 30 ℃ for reaction for 90min;
(3) And (3) dropwise adding 100mL of 0.1g/mL polyaluminium chloride into the mixture system obtained in the step (2) under the stirring condition, wherein the stirring speed is 2000-4000 rpm, and the stirring speed is 200-500 rpm after the addition is finished, and carrying out precipitation reaction for 10min.
(4) And (3) carrying out suction filtration on the mixture system obtained in the step (3), and separating solid and liquid to obtain solid organic sediment and alkaline recovery liquid.
The alkali impregnation waste liquid of the example of the present application was subjected to the following treatment, wherein the content of each main component (the content value of each main component was measured by liquid chromatography) and the pH change were as shown in table 5 below:
TABLE 5
Comparison of examples 3, 4 and 5 shows that better separation results can be obtained by adding lithium chloride to the alkaline waste liquor than by adding calcium chloride and sodium chloride to the alkaline waste liquor.
The foregoing examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (6)
1. The chemical alkali recovery treatment process of the chemical pulp waste liquid is characterized by comprising the following steps of:
adding a pretreatment reagent into the chemical mechanical pulp waste liquid to perform pretreatment reaction, and obtaining a first mixture system after the pretreatment reaction is completed; the pretreatment reagent is at least one of a hydrophobic modifier, a free radical reaction initiator and a metal ion salting-out agent; the pH value of the chemical mechanical pulp waste liquid is 12-14; the hydrophobic modifier is at least one of silane coupling agent, 1, 2-alkylene oxide and alkenyl succinic anhydride; the free radical reaction initiator is at least one of persulfates, azo compounds and hydroperoxides; the metal ion salting-out agent is at least one of sodium chloride, potassium chloride and lithium chloride;
adding a flocculating agent into the first mixture system to carry out a precipitation reaction, and obtaining a second mixture system after the precipitation reaction is completed; the flocculant is at least one of polyaluminum chloride, cationic polyacrylamide and ferric trichloride;
carrying out solid-liquid separation on the second mixture system to obtain solid organic sediment and alkaline recovery liquid; the pH value of the alkaline recovery liquid is 11.8-13.
2. The chemical alkali recovery treatment process of the chemical pulp waste liquid according to claim 1, wherein the silane coupling agent is at least one of gamma-chloropropyl triethoxysilane, gamma-chloropropyl methyl dichlorosilane, gamma-chloropropyl trimethoxysilane, gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane.
3. The chemical alkali recovery treatment process of a chemical pulp waste liquid according to claim 1, wherein the persulfate is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
4. The chemical alkali recovery treatment process of the chemical pulp waste liquid according to claim 1, wherein the addition amount of the hydrophobic modifier is 10-20 g/L; and/or
The addition amount of the free radical reaction initiator is 5-15 g/L; and/or the adding amount of the metal ion salting-out agent is 5-15 g/L.
5. The chemical alkali recovery treatment process of chemical pulp waste liquid according to claim 1, wherein the adding amount of the flocculating agent is 0.1-0.4 g/L.
6. The chemical alkali recovery treatment process of a chemical pulp waste liquid according to any one of claims 1 to 5, wherein the pretreatment reaction is carried out at a temperature of 30 to 90 ℃ for 30 to 90min.
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| CN202211017370.7A CN115434178B (en) | 2022-08-23 | 2022-08-23 | Chemical alkali recovery treatment process for chemical mechanical pulp waste liquid |
| PCT/CN2022/121173 WO2024040677A1 (en) | 2022-08-23 | 2022-10-18 | Chemical alkali recovery treatment process for chemimechanical pulping waste liquid |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724414A (en) * | 2005-06-24 | 2006-01-25 | 华南理工大学 | Process for biological decolouring of waste water of pulping |
| CN101215797A (en) * | 2008-01-04 | 2008-07-09 | 金东纸业（江苏）股份有限公司 | Zero discharge treatment method for chemical mechanical pulp |
| CN102249436A (en) * | 2011-07-13 | 2011-11-23 | 浙江开创环保科技有限公司 | Method for concentrating CMP (chemi-mechanical pulp) waste liquid by using membrane process |
| CN102392381A (en) * | 2011-08-02 | 2012-03-28 | 华南理工大学 | Chemi-mechanical pulp waste liquid alkaline recycling pretreatment method |
| CN102758375A (en) * | 2012-07-31 | 2012-10-31 | 广西金桂浆纸业有限公司 | Pretreatment method of chemical-mechanical pulping effluent |
| CA2877756A1 (en) * | 2012-06-25 | 2014-01-03 | Beijing Insight Biomass Llc | Chemical pulping method |
| CN105883946A (en) * | 2016-06-22 | 2016-08-24 | 南京永禾环保工程有限公司 | Compound water purifying agent for deep treatment of chemimechanical pulp effluents and preparation method of compound water purifying agent for deep treatment of chemimechanical pulp effluents |
| CN112048933A (en) * | 2020-09-07 | 2020-12-08 | 齐鲁工业大学 | Method for producing chemi-mechanical pulp and semi-chemical pulp |
| CN114180782A (en) * | 2021-11-25 | 2022-03-15 | 中国制浆造纸研究院有限公司 | Method for treating waste liquor of pulping of moso bamboo chemi-mechanical pulp |
| CN114291930A (en) * | 2021-12-30 | 2022-04-08 | 海南金海浆纸业有限公司 | Treatment method of boiler washing wastewater of sulfate pulping alkali recovery boiler |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397684A (en) * | 2001-07-13 | 2003-02-19 | 阮键华 | Method for treating and comprehensively utilizing black liquor of alkaline pulping and paper making |
| CN101891290A (en) * | 2010-07-15 | 2010-11-24 | 中国林业科学研究院林产化学工业研究所 | Composite purifying agent used for chemical-mechanical pulp advanced waste water treatment and preparation method thereof |
| CN102659290B (en) * | 2012-05-25 | 2013-12-25 | 中国林业科学研究院林产化学工业研究所 | Method for advanced treatment of high-concentration chemi-mechanical pulp effluent by catalytic oxidation |
| CN103388275B (en) * | 2013-07-24 | 2015-11-04 | 宜宾海丝特纤维有限责任公司 | The pretreating process of Black Liquor by Electrodialysis alkali collection during a kind of pulp manufactures |
| CN103469664B (en) * | 2013-08-26 | 2015-09-16 | 陕西科技大学 | A kind of alkali collection workshop section green liquor flocculation silicon removing method |
| WO2019241413A1 (en) * | 2018-06-12 | 2019-12-19 | Domtar Paper Company, Llc | Methods and processes for lignin isolation/extraction |
| CN109160591A (en) * | 2018-09-29 | 2019-01-08 | 中国林科院林产化工研究所南京科技开发总公司 | A kind of drop coagulant preparation of reducing rules Sewage advanced treatment and application |
| CN115467182B (en) * | 2022-08-23 | 2024-01-05 | 天津科技大学 | Pretreatment process for pulp production raw materials |
-
2022
- 2022-08-23 CN CN202211017370.7A patent/CN115434178B/en active Active
- 2022-10-18 WO PCT/CN2022/121173 patent/WO2024040677A1/en unknown
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724414A (en) * | 2005-06-24 | 2006-01-25 | 华南理工大学 | Process for biological decolouring of waste water of pulping |
| CN101215797A (en) * | 2008-01-04 | 2008-07-09 | 金东纸业（江苏）股份有限公司 | Zero discharge treatment method for chemical mechanical pulp |
| CN102249436A (en) * | 2011-07-13 | 2011-11-23 | 浙江开创环保科技有限公司 | Method for concentrating CMP (chemi-mechanical pulp) waste liquid by using membrane process |
| CN102392381A (en) * | 2011-08-02 | 2012-03-28 | 华南理工大学 | Chemi-mechanical pulp waste liquid alkaline recycling pretreatment method |
| CA2877756A1 (en) * | 2012-06-25 | 2014-01-03 | Beijing Insight Biomass Llc | Chemical pulping method |
| CN102758375A (en) * | 2012-07-31 | 2012-10-31 | 广西金桂浆纸业有限公司 | Pretreatment method of chemical-mechanical pulping effluent |
| CN105883946A (en) * | 2016-06-22 | 2016-08-24 | 南京永禾环保工程有限公司 | Compound water purifying agent for deep treatment of chemimechanical pulp effluents and preparation method of compound water purifying agent for deep treatment of chemimechanical pulp effluents |
| CN112048933A (en) * | 2020-09-07 | 2020-12-08 | 齐鲁工业大学 | Method for producing chemi-mechanical pulp and semi-chemical pulp |
| CN114180782A (en) * | 2021-11-25 | 2022-03-15 | 中国制浆造纸研究院有限公司 | Method for treating waste liquor of pulping of moso bamboo chemi-mechanical pulp |
| CN114291930A (en) * | 2021-12-30 | 2022-04-08 | 海南金海浆纸业有限公司 | Treatment method of boiler washing wastewater of sulfate pulping alkali recovery boiler |
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