WO2016179846A1 - 一种全棉秸秆化机浆制浆废液的零排放工艺 - Google Patents

一种全棉秸秆化机浆制浆废液的零排放工艺 Download PDF

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WO2016179846A1
WO2016179846A1 PCT/CN2015/079084 CN2015079084W WO2016179846A1 WO 2016179846 A1 WO2016179846 A1 WO 2016179846A1 CN 2015079084 W CN2015079084 W CN 2015079084W WO 2016179846 A1 WO2016179846 A1 WO 2016179846A1
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washing
pulp
waste liquid
raw material
dosing
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PCT/CN2015/079084
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English (en)
French (fr)
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白博
王勇
刘玉芳
白嘉妮
史晓菲
白伟才
安骏
薛希贤
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白博
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/26—Multistage processes
    • 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
    • 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
    • D21C11/0014—Combination of various pulping processes with one or several recovery systems (cross-recovery)
    • 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
    • D21C11/10—Concentrating spent liquor by evaporation
    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • 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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/18—De-watering; Elimination of cooking or pulp-treating liquors from the pulp

Definitions

  • the invention relates to the field of pulping and papermaking, in particular to a zero-discharge process of a cotton straw sizing pulp pulping waste liquid.
  • the zero discharge of chemical pulping wastewater is a development direction.
  • the front end extraction of pulping waste liquid and the enrichment by evaporation and then the utilization of the evaporation residual liquid are to achieve zero discharge of cotton straw pulping pulping waste liquid. An effective way.
  • the residual liquid is concentrated to a combustion furnace for alkali recovery, and the condensed water is evaporated to be used in the pulping section.
  • the ton of pulp actually consumes 2 tons of clean water, which is mainly consumed in the evaporation and drying of the pulp. Since 2005, some chemical pulp mills in North America and Europe, including Chetwynd BC and REARI JOUTSE NO MILL in Nordic Finland, M-REAI KASKIN NO MILL and STORA EN-SO FORS in Sweden have realized the chemical recovery process. Zero discharge of pulp wastewater.
  • the solid matter burning value in the chemical pulp wastewater is determined to be 12.86 ⁇ 13.84MJ/kg, and the general carbohydrate burning value is 12.6MJ/kg, which indicates that the burning value of the solid waste of the chemical pulp wastewater is similar to that of the general carbohydrate, which is suitable for burning.
  • the alkali recovery treatment is carried out.
  • the invention patent "Zero Discharge Waste Discharge Zero Discharge Treatment Method (Patent No. CN200810019354.5)" discloses a chemical machine slurry waste liquid zero discharge treatment method, which comprises the following steps: firstly, a concentration of 2% chemical pulp waste liquid Pre-concentration by membrane separation, 80% of the permeate is reused in the pulping and alkali recovery section, and the filtrate concentration of 20% of the total wastewater is 10%, which is sent to the multi-effect evaporation station for further evaporation and concentration. Concentrated residue The alkali is recovered, and the distilled water is used for pulping after further stripping.
  • the invention can realize the zero discharge of the chemical pulp by the alkali filtration process by using the membrane filtration to concentrate the pulp waste liquid, but the membrane filtration increases the investment and the operation and maintenance cost, and at the same time, the water concentration of the chemical pulp is still low. Big problem.
  • the invention patent "Chemical mechanical pulp wastewater zero discharge treatment method (Patent No. 200910231012.4)” discloses a waste water zero discharge treatment method for preparing alkaline hydrogen peroxide mechanical pulp (APMP).
  • the specific steps involved are: a distillation concentration process and an alkali recovery process.
  • the wastewater from the chemical pulping system concentration of 1.5 to 2.0% is concentrated and concentrated by a mechanical vapor recompression evaporator to a concentration of 5 to 8%, and then 12-15%, and the cooking waste generated by the chemical pulp method
  • the liquid mixture is sent to the alkali recovery section to be concentrated to 50% and then burned, and the condensed water is used for pulp washing.
  • the invention can realize the zero discharge of the chemical pulp waste liquid by distilling the chemical pulp waste liquid by distillation, but because the sewage concentration is low, 1.5 to 2%, the wastewater generated during the pulping process of the chemical pulp is still relatively large.
  • the pulp alkali recovery of the chemical machine can be treated with reference to the experience of chemical pulp alkali recovery, but it must solve the problem that the chemical pulp concentration is low (2%) and the water volume is relatively large, resulting in high alkali recovery operation cost.
  • the invention patent "recycling method in straw pulping and papermaking process (201010126189.0)”, that is, “spring forest mode”, is to produce chemical pulp by using non-wood fiber as raw material, pulping wastewater is multi-effect evaporation concentrated, concentrated residue is used for The production of fertilizer or alkali lignin opens up the road to the utilization of pulping waste liquid.
  • the invention relates to a recycling method in a straw pulping and papermaking process, that is, a non-wood fiber raw material and a waste material for pulping are obtained by preparing a raw material; a non-wood fiber raw material is cooked by an ammonium sulfite method to obtain a crude pulp; The slurry is obtained into a slurry and a concentrated black liquor; the slurry is washed and then post-treated to obtain a pulp and a black liquor for preparing a paper product; the concentrated black liquor and the diluted black liquor are mixed and evaporated to concentrate, and the evaporated liquid is recovered to obtain a sewage condensed water.
  • the residual concentrate is used as a fertilizer raw material or a concentrated black liquor for preparing fertilizer; the sewage condensed water is mixed with one or more of the waste materials, crop by-products or organic waste obtained from the preparation, and the nitrogen source or ammonium sulfite of the sewage condensed water is utilized. Fermentation to obtain a substrate or fertilizer; or to use sewage condensed water for flue gas desulfurization, wherein ammonia reacts with the flue gas to obtain a cooking agent ammonium sulfite, and the recycled water after the middle water treatment is used for the corresponding part of the entire pulp process, thereby achieving The comprehensive utilization of grass straw provides a new bright spot for the circular economy.
  • the invention patent does not address the problem of wastewater treatment of bleached pulp of non-wood fibers (including cotton straw).
  • the solid content of wastewater was increased from 4.36% to 6.7%, and when the extraction rate of wastewater was 95%, the water consumption per ton of pulp was 1910.84 kg.
  • the technical process adopts two-stage impregnation treatment, and the high-concentration mixer is used to mix the subsequent squeezed wastewater with the medicament and pulp before the second stage of impregnation.
  • the subsequent squeezing wastewater is derived from the wastewater produced by the washing of the high consistency pulp from the high concentration bleaching tower.
  • the pollutants of the general wood pulping wastewater mainly come from the organic compounds dissolved from the fiber raw materials in the production process, the residual chemicals in the process engineering and the lost fine fibers.
  • the main chemical components of the organic matter are lignin degradation products polysaccharides and organic acids, among which lignin degradation products are 30-40%, polysaccharides 10-15%, and organic acids account for 35-40%.
  • steaming, extrusion tearing or twisting, impregnation, refining, washing and other steps gradually push the raw materials into the process of pulping, and then gradually remove the pollution source until the end of the process , to achieve qualified products for pulp bleaching.
  • the production amount and concentration of chemical pulp wastewater are related to the pulping process, and the conventional mechanical pulping process adopts high-concentration bleaching to extract sewage, resulting in large water volume and low concentration.
  • the pulping waste liquid of the cotton straw bleaching machine pulp is more difficult to handle than the general wood pulping machine.
  • the present invention combines the problem of whiteness of cotton straw sizing pulp with zero discharge of pulping wastewater, and starts from pigmentation and pigment separation of cotton straw raw materials, through reverse Washing, front-end extraction to achieve bleaching of cotton straw pulping and on-line high-concentration extraction of pulping waste liquid, and further concentration of pulping waste liquid by conventional evaporation and concentration, condensed water is reused in pulping process, and concentrated residue Zero emissions through comprehensive utilization.
  • a zero-discharge process for cotton straw sizing pulp pulping waste liquid comprising a pulp bleaching process and a comprehensive utilization process of pulp bleaching wastewater reuse, characterized by: online concentration and high-concentration extraction of pulping waste liquid and Subsequent evaporation concentration, evaporation condensate reuse and evaporation of residual liquid resources to achieve zero discharge of pulping waste liquid.
  • On-line concentration and high-concentration extraction of pulping waste liquid that is, pigmentation decomposition of cotton stalk raw materials in the pulping process - pigment separation, reverse washing and front end extraction.
  • the preferred process flow is: raw material washing (a) - raw material cooking (b) - extrusion (c1) - washing (d1) - silk (e1) - dosing (f1) - - impregnation (g1) - washing (h1) - high consistency refining (i1) - dosing (j1) - impregnation (bleaching) (k1) - washing (l1) - high consistency refining (m1) - washing (n1).
  • extrusion (c1) - washing (d1) - silk (e1) - dosing (f1) four processes are completed on a spinning machine, the preferred process flow is: raw material washing ( a) - raw material cooking (b) - extrusion washing silk silk dosing (cdef2) - impregnation (g2) - washing (h2) - high consistency refining (i2) - dosing (j2 ) - impregnation (bleaching) (k2) - washing (l2) - high consistency refining (n2) - washing (o2).
  • the preferred process is: raw material washing (a)- - Raw material cooking (b) - Extrusion washing and silking dosing (cdef3) - Impregnation (g3) - Washing (h3) - Extrusion washing, Filament, dosing (i3) - Impregnation (j3 ) - washing (k3) - high consistency refining (l3) - dosing (m3) - impregnation (bleaching) (n3) - washing (o3) - high consistency refining (p3) - - Washing as (q3).
  • pigmentation - pigment extraction is in the raw material cooking (b) - extrusion washing and silking (cdef3), impregnation (g3) - washing (h3) to squeeze washing and silk
  • the drug (i3) link, impregnation (j3) - washing (k3) is completed. That is, it is completed in the raw material cooking (b3)
  • the pigment is decomposed, and the pigment extraction is completed by the waste liquid extraction in the step of extrusion washing and squeezing and squeezing (cdef3); further, the pigmentation is further completed in the immersion (g3) step, and the waste is passed in the washing (h3) step.
  • the liquid is extracted, and then the extrusion and washing are completed in the step of the extrusion washing and silking (i3), and the pigment extraction is further completed by the waste liquid extraction; further, the pigmentation is completed on the impregnation (j3) step, and the slurry is washed (k3).
  • the pigment extraction is further completed by waste liquid extraction.
  • the reverse washing is done by washing (q3) - dosing (m3) and washing (o3), further by washing (o3) - squeezing and washing (cdef3) and Washing (k3) is completed on the link. That is, the washing water (q3) is completed with clean water, and the waste liquid generated by washing (q3) is used for dispensing and washing (3) of the dosing (m3); and the waste liquid generated by the slurry washing (o3) is used for squeezing Dosing and washing (k3) of pressure-washed pulp silk dosing (i3).
  • the front end extraction is in the process of extrusion washing, squeezing and squeezing (cdef3), washing (h3), and squeezing and washing (i3), washing (k3), and extracting pulp waste. liquid.
  • the extrusion washing and squeezing squeezing (h4)-impregnation (i4) is added, and the preferred process is: raw material washing (a) - raw material cooking (b) - -Extrusion washing and silking dosing (cdef4) - impregnation (g4) - extrusion washing and silking dosing (h4) - impregnation (i4) - washing (j4) - high consistency refining (k4) - dosing (l4) - impregnation (bleaching) (m4) - washing (n4) - high consistency refining (o4) - washing (p4).
  • pigmentation - pigment extraction is in the raw material cooking (b4) - extrusion washing and silking (cdef4), impregnation (g4) - extrusion washing and silking (h4), Impregnation (i4) - washing (j4) is completed. That is, the pigmentation is completed in the raw material cooking (b4), and the pigment extraction is completed by the waste liquid extraction in the step of the extrusion washing and squeezing (cdef4); further, the pigmentation is further completed in the immersion (g4) step.
  • the extrusion and washing are completed and the pigment extraction is further completed by the waste liquid extraction; further, the pigmentation is completed on the impregnation (i4) link, and the pigmentation is carried out in the step of washing (j4).
  • the waste liquid extraction further completes the pigment extraction.
  • the reverse washing is done by washing (p4) - dosing (l4) and washing (n4), and then by washing (n4) - squeezing and washing (h4) and Washing (j4) is completed on the link. That is, the washing water (p4) is completed with clean water, and the waste liquid produced by washing (p4) is used for dosing (l4). Dispensing and washing (n4); further, the waste liquid produced by the slurry washing (n4) is used for the dosing and washing (j4) of the extrusion washing and silking (h4).
  • front end extraction is to extract the pulping waste liquid in the steps of extrusion washing and silking (cdef4), extrusion washing and silking (h4) and washing (j4).
  • the raw material washing (1) process removes the sediment in the raw material by washing, and the raw material concentration is 5%.
  • the raw material washing step (a) is replenished with recycled water.
  • the raw material cooking (b) process is a preliminary decomposition of the cotton stalk material by a continuous or batch digester.
  • the cooking process conditions are: temperature 60-120 min, medicament: alkaline oxide 1-4%, so that the chemical liquid fully saturates the cotton stalk raw material to reach a saturated slurry concentration of 25-30%.
  • the raw material cooking step (b) is replenished with recycled water.
  • the step of squeezing the washing and silking is to sequentially complete the four steps of extrusion, washing, twisting and dosing on the same spinning machine.
  • a washing liquid injection hole and a waste liquid discharge port are exclusively provided on the thread rolling machine.
  • the slurry is concentrated by 20-30%, and the washing and the drug dilution are completed by using the condensed water and the reverse washing water.
  • each impregnation step in the entire process is completed at the same time bleaching, fiber softening and complete decomposition of the macropigmentation and general fouling.
  • the impregnation is carried out under the condition of holding in the reaction chamber, and the process conditions are: temperature 60-95 ° C, heat preservation 60-150 min.
  • washing the pulp each impregnation step in the whole process flow is to complete the pigment extraction and general pollutant extraction by washing the sewage, and control the pulp concentration according to the process requirements.
  • the washing is completed on the extruder, and the concentration is 8 to 25%, and the pulping concentration is 30 to 55%.
  • the washing is replenished with recycled water and reverse washing back.
  • the amount of secondary extrusion washing and silking dosing agent hydrogen peroxide 4 to 6% (100% purity), basic oxide (100% purity) 2 to 5% raw material weight percentage, stabilizer 2 to 4% Chelating agent 0.5 to 1%, MgSO4 0.05%, and the slurry concentration is 20 to 30%, and the washing and the drug dilution are completed by replenishing the condensed water and the reverse washing water.
  • the evaporation concentration is completed at the multi-effect evaporation station, and the high-concentration pulp waste liquid extracted from the online front end is further concentrated, and the separated condensed water and the evaporated residual liquid are separately used for pulping and comprehensive utilization.
  • the condensed water is reused, that is, the condensed water flows out from the multi-effect evaporation station, and is all reused for the raw material washing, the raw material cooking, and the bleaching and dosing.
  • the condensed water is clear condensed water and turbid condensed water.
  • the water temperature is above 60 ° C.
  • the COD of the condensed water is generally 400-600 mg/L, and the COD is 900-1200 mg/L.
  • the condensed water reuse direction is: raw material washing (a), raw material cooking (b), washing (d1), dosing (f1), washing (h1).
  • the condensed water reuse direction is: raw material washing (a), raw material cooking (b), extrusion washing and silking dosing (cdef2), washing (h2).
  • the condensed water reuse direction is: raw material washing (a), raw material cooking (b), squeeze washing and silking dosing (cdef3), washing (h3), extrusion washing and silking dosing (i3 ), washing (k3) link.
  • the condensed water reuse direction is: raw material washing (a), raw material cooking (b), extrusion washing and silking dosing (cdef4), extrusion washing and silking dosing (i4), washing (k4 ) link.
  • the use of the evaporation residue for resource utilization includes the production of fertilizer, alkali lignin or alkali recovery by evaporation of the residual liquid.
  • KOH is selected as the basic oxide, and a sodium-free stabilizer is used.
  • the concentration of chemical pulping wastewater is high and the water volume is small, which facilitates evaporation and concentration of pulping wastewater;
  • the evaporated condensate is recycled to the raw material for washing, raw material cooking, and raw material impregnation and bleaching.
  • the pulping waste liquid is recycled and utilized, so as to achieve zero discharge of the chemical pulping waste liquid.
  • Raw material cotton straw, origin: Liaocheng area, Shandong province
  • raw material washing (a) - raw material cooking (b) - extrusion washing and silking dosing (cdef4) - impregnation (g4) - extrusion washing and silking dosing (h4) - impregnation (i4) - washing (j4) - high consistency refining (k4) - dosing (l4) - impregnation (bleaching) (m4) - washing (n4) - high concentration grinding Pulp (o4) - washing (p4).
  • Raw material washing (a). In a 10,000-ton/year drum-type raw material scrubber, the raw material concentration was 5%, and the raw material washing water was replenished with COD at 1100 mg/L of recycled mixed evaporating condensed water. The water content of the cotton stalk raw material storage state is 14%, and the water content after washing is 60%. In the raw material washing step, except for removing a small amount of water from the sediment, only the water is replenished, and no waste water is discharged. The water replenishment mainly comes from the evaporation condensate of the seven-effect evaporation station of Shandong Quanlin Paper Co., Ltd., which is adjacent to Shandong Kailong Paper Technology Co., Ltd.
  • Raw material cooking (b).
  • the cooking of the raw materials is carried out under the condition that the raw materials are sufficiently absorbed.
  • the process conditions are as follows: temperature is 95 ° C, time is 60 min, NaOH (100% purity) 2%, and the amount is the weight percentage of the raw materials.
  • the water content of the raw material before cooking is 60%, and the water content at the end of cooking is 30%.
  • the water is reused by the recycled COD at 1100 mg/L of sewage condensed water, and no waste water is discharged.
  • the cooking make-up water comes from evaporating condensate.
  • squeeze the washing machine pulp silk dosing (cdef4).
  • the extrusion washing and squeezing of the silk thread is sequentially carried out on the reeling machine.
  • the generated wastewater is mixed with the effluent discharged from the extrusion section and discharged from the reeling machine, and is collected as a front-end extraction pulping wastewater to be evaporated and concentrated.
  • the COD extracted from the squeeze washer pulping (cdef3) was: 47,321 mg/L.
  • the dosage of the agent is: hydrogen peroxide (100% purity) 4%
  • dosage of the agent NaOH (100% purity) 4%, Na 2 SiO 3 4%, TDPA 0.3%, penetrant 0.3%, MgSO 4 0.01%
  • dosage Both are raw material weight percentage, and the pulp concentration is 25%.
  • Impregnation (g3). The condition is: heat preservation at 95 ° C in a 1# bleaching reaction chamber for 120 min.
  • the dosage of the agent is: hydrogen peroxide (100% purity) 6%
  • dosage of the agent NaOH (100% purity) 4%, Na 2 SiO 3 4%, TDPA 0.05%, penetrant 0.05%, MgSO 4 0.01%
  • dosage Both are raw material weight percentage, and the pulp concentration is 25%.
  • Impregnation (i4) conditions The conditions are: heat preservation at 95 ° C in a 2# bleaching reaction chamber for 120 min.
  • Washing (j4) Finished in the extruder. The imported pulp is 20% concentrated and the export pulp is 40% thick. The supplementary squeezing water is derived from the reverse washing of the waste liquid generated from the washing (o4). The wastewater generated by the washing (j4) is collected as a front end and then concentrated by evaporation. Washing water (j4) extracted wastewater COD: 54732mg / L.
  • dosing (l4). Adding the mixed medicament at the outlet of the high-concentration refiner and the washing waste liquid discharged from the slurry washing (p4) as the medicament dilution water, the slurry concentration is 30%, and the dosage of the medicament is: hydrogen peroxide (2% pure) NaHO1%, Na 2 SiO 3 1%, DTPA 0.2%, MgSO 4 0.01%.
  • Impregnation (bleaching) (m4). The condition is: heat preservation at 95 ° C in a 3# bleaching reaction chamber for 120 min.
  • washing (n4) The imported pulp is 12% concentrated, the export pulp is 35% thick, the washing water is derived from washing (p4), and the squeezing waste liquid is used for squeezing washing and sizing (h4) dilution water and washing (j4).
  • the process conditions of raw material cooking (b) are: temperature 40 ° C, time 120 min, NaOH 2%.
  • the raw material cooking (b) has the following conditions: temperature is 99 ° C, time is 120 min, and NaOH is 1%.
  • the process conditions of extrusion squeezing and sizing are: 5% hydrogen peroxide, dosage: basic oxide (100% purity) 4% by weight of raw materials, Na 2 SiO 3 4%, DTPA 0.3% , MgSO 4 0.05%, the pulp concentration is 25%.
  • the process conditions of squeezed slurry washing and silking are: 7% hydrogen peroxide, dosage of the agent: basic oxide (100% purity) 4% by weight of raw materials, Na 2 SiO 3 4%, DTPA 0.3% , MgSO 4 0.05%, the pulp concentration is 25%.
  • the dosing process of extrusion squeezing and squeezing sputum is: hydrogen peroxide 4%, dosage: basic oxide (100% purity) 4% raw material weight percentage, Na 2 SiO 3 4%, DTPA0. 3%, MgSO 4 0.05%, and the pulp concentration was 25%.
  • the dosing process of extrusion squeezing and squeezing sputum is: 5% hydrogen peroxide, dosage of the agent: basic oxide (100% purity) 4% by weight of raw materials, Na 2 SiO 3 4%, DTPA0. 2%, MgSO 4 0.05%, pulp concentration 25%.
  • the process conditions of extrusion squeezing and laminating (h4) are: 7% hydrogen peroxide, dosage of the agent: basic oxide (100% purity) 4% by weight of raw materials, Na 2 SiO 3 4%, DTPA 0.2% , MgSO 4 0.05%, the pulp concentration is 25%.
  • the process conditions of dosing (l4) are: hydrogen peroxide (100% purity) 3%, dosage of the agent: basic oxide (100% purity) 1% by weight of raw materials, Na 2 SiO 3 1%, DTPA 0.1%, MgSO 4 0.01%, the pulp concentration is 25%.
  • the process conditions of dosing (i) are: hydrogen peroxide (100% purity) 4%, dosage of the agent: basic oxide (100% purity) 1.5% by weight of raw materials, Na 2 SiO 3 1%, DTPA 0.1%, MgSO 4 0.01%, the pulp concentration is 25%.
  • the process adopted is: raw material washing (a) - raw material cooking (b) - extrusion washing and silking dosing (cdef3) - impregnation (g3) - washing (h3) - extrusion washing Filament dosing (i3) - impregnation (j3) - washing (k3) - high consistency refining (l3) - dosing (m3) - impregnation (bleaching) (n3) - washing ( O3) - high consistency refining (p3) - washing as (q3).
  • the process conditions of washing (h3) are as follows: the washing slurry is completed on a single-screw machine, the imported pulp is 20% concentrated, and the outlet pulp is 42% concentrated.
  • the process parameters of the other links are the same as in Example 1.
  • Pulp brightness prepared in Examples 2 to 11 is greater than 80% ISR, dust of: when ⁇ 0.3cm 2, less than 550 / m 2; when 0.3 ⁇ 1.0cm 2, less than 18 / m 2, the other physical properties
  • the indicator can meet the production requirements of printing paper.

Abstract

一种全棉秸秆化机浆制浆废液的零排放工艺，首先对制浆废液进行前端高浓提取，然后对高浓制浆废液蒸发浓缩，对蒸发冷凝水回用，对蒸发残液进行资源化利用，最终实现制浆废液的零排放。制浆废液的前端高浓提取包括在挤压洗浆搓丝加药、洗浆环节提取制浆废液。

Description

一种全棉秸秆化机浆制浆废液的零排放工艺 技术领域
本发明涉及制浆造纸领域，具体涉及一种全棉秸秆化机浆制浆废液的零排放工艺。
技术背景
化机浆制浆废水的零排放是一个发展方向，对制浆废液进行前端提取并通过蒸发浓缩然后对蒸发残液进行资源化利用则是实现全棉秸秆化机浆制浆废液零排放的有效途径。
据《江苏造纸》2013年3月第一期总第98期房桂干“我国化机浆废水处理技术的发展”的文章介绍，上世纪80年代加拿大制浆造纸研究所首次提出化机浆废水零排放的概念，之后Meadow Lake Pulp Ltd在世界上首次采用碱回收技术实现化机浆废液的零排放。该公司用白杨做原料生产BCTMP化机浆，年产28.5万吨，吨浆废水10m3，浓度2％。采用三台压汽蒸发器将废液浓度从2％浓缩到35％，然后采用三效浆膜增浓器增浓致67％。浓缩残液至燃烧炉燃烧进行碱回收，蒸发冷凝水回用于制浆工段。吨浆实际消耗清水2吨，主要消耗在纸浆的蒸发干燥上。2005年以来北美、欧州的一些化机浆厂，包括Chetwynd BC和北欧芬兰的REAI JOUTSE NO MILL，M-REAI KASKIN NO MILL公司和瑞典的STORA EN-SO FORS公司采用碱回收工艺，实现了化机浆废水的零排放。
经测定化机浆废水中固形物燃烧值12.86～13.84MJ/kg,一般碳水化合物燃烧值为12.6MJ/kg,表明化机浆废水固形物燃烧值和一般碳水化合物燃烧值相接近，适合通过燃烧进行碱回收处理。
发明专利“化机浆废液零排放处理方法(专利号CN200810019354.5)”公开了一种化机浆废液零排放处理方法，包括以下步骤：首先将浓度为2％的化机浆废液采用膜分离预浓缩，80％的透过液回用于制浆和碱回收工段，占总废水量20％的滤出液浓度达到10％，送入多效蒸发站进一步蒸发浓缩。浓缩残渣进行传 统碱回收，蒸馏水经进一步汽提后回用于制浆。该发明可以通过膜过滤对制浆废液浓缩实现对化机浆采用碱回收工艺实现化机浆零排放，但是膜过滤增加投资和运行维护成本，同时仍存在化机浆污水浓度低耗水量较大的问题。
发明专利“化学机械浆废水零排放处理方法(专利号200910231012.4)”公开了一种制备碱性过氧化氢机械浆(APMP)的废水零排放处理方法。其包含的具体步骤为：蒸馏浓缩工艺和碱回收工艺。对来自化机浆系统浓度为1.5～2.0％的废水经机械蒸汽再压缩式蒸发器两级分级蒸发浓缩至浓度达到5～8％，进而达到12-15％后与化学浆法产生的蒸煮废液混合送到碱回收工段浓缩到50％后燃烧，冷凝水用于纸浆洗涤。该发明可以通过蒸馏对化机浆废液浓缩实现化机浆废液的零排放，但因污水浓度低，1.5～2％，仍存在化机浆制浆过程中废水产生量仍比较大。
综上所述，化机浆碱回收可以借鉴化学浆碱回收的经验进行处理，但必须解决化机浆浓度低(2％)、水量相对较大从而造成碱回收运行成本高的问题。
发明专利“秸秆制浆造纸过程中的循环利用方法(201010126189.0)”，即“泉林模式”，是以非木纤维为原料生产化学浆，制浆废水采用多效蒸发浓缩，浓缩残液用于生产肥料或碱木素，开辟了制浆废液资源化利用的道路。具体为：该发明涉及秸秆制浆造纸过程中的循环利用方法，即通过备料得到用于制浆的非木材纤维原料和废料；非木材纤维原料采用亚硫酸铵法蒸煮得到粗浆；粗浆挤浆得到浆料和浓黑液；浆料洗涤后后处理得到用于制备纸制品的纸浆和稀黑液；浓黑液和稀黑液混合蒸发浓缩，蒸发出的液体经回收得到污冷凝水，残留浓缩物作为肥料原料或用于制备肥料的浓黑液；污冷凝水与备料所得的废料、农作物副产品或有机废弃物的一种或几种混合，利用污冷凝水的氮源或亚硫酸铵发酵得到基质或肥料；或将污冷凝水用于烟气脱硫，其中的氨与烟气反应得到蒸煮剂亚硫酸铵，中段水处理后的回用水用于整个纸浆过程的相应部位，从而达到禾草类秸秆的综合利用，为循环经济提供新的亮点。但是该发明专利没有涉及到非木纤维(包括棉秸秆)漂白化机浆的废水处理问题。
南京林业大学徐家祥硕士研究生学位论文《化机浆废水循环增浓技术》，论文针对化机浆废水送碱回收时固形物浓度较低，0.8～2％，导致蒸发浓缩时消耗能量过多这一问题，研究了一种新的PRC-APMP制浆新流程，通过在传统PRC-APMP制浆流程漂白塔后增加四台串联的双螺旋挤压机，通过高浓、逆流的方式提取漂白废水，废水一部分送碱回收处理，另一部分循环回用在高浓混合器中用做配制漂白药液。在改进后的PRC-APMP流程中将废水固含量由4.36％提高至6.7％，吨浆废水提取率在95％时，吨浆提取用水量为1910.84kg。该技术工艺流程采用两段浸渍处理，在第二段浸渍前采用高浓混合器将后续挤浆废水回用和药剂、纸浆混合。后续挤浆污水来源于从高浓漂白塔出来的高浓纸浆的进行洗涤产生的废水。但经过实验证明，该技术仍无法解决棉秸秆原料化机浆的白度问题。
专利“两步隔离式全无氯全棉秆漂白化机浆清洁生产工艺(专利号：ZL200810238434.X)”通过两步浸渍漂白实现了较高的棉秆化机浆成浆白度，达到81.3％ISO，实现了对以棉秆为原料进行工业化生产高白度漂白化机浆的技术突破，但未涉及制浆废水的处理问题。
根据漂白化机浆的制浆机理，一般木材化机浆废水的污染物质主要来源于生产过程中从纤维原料中溶出的有机化合物，工艺工程中残余的化学品和流失的细小纤维。其有机物主要化学成分是木质素降解产物多糖和有机酸等，其中木质素降解产物30～40％，多糖10～15％，有机酸占35～40％。通过机械的和化学的工艺方法经汽蒸、挤压撕裂或搓丝、浸渍、磨浆、洗浆等环节对原料逐步在成浆的过程中进行污染源的逐步分解分离提出，直到工艺流程结束，达到成浆漂白的合格产品。并且化机浆废水的产生量和浓度与制浆工艺相关联，传统化机浆工艺采取高浓漂白后提取污水，结果造成水量大，浓度低。
全棉秸秆漂白化机浆的制浆废液比一般木材化机浆更加难以处理。
发明内容
为克服以上存在的问题和局限，本发明从解决棉秸秆化机浆白度问题和制浆废水零排放相结合，从全棉秸秆原料的色素分解和色素分离入手，通过逆向 洗涤、前端提取实现棉秸秆化机浆的漂白和制浆废液的在线高浓提取，并通过传统的蒸发浓缩实现制浆废液的进一步浓缩，冷凝水回用于制浆过程，对浓缩残渣通过综合利用实现零排放。
具体为：
一种全棉秸秆化机浆制浆废液的零排放工艺，包括制浆漂白工序和制浆漂白废水回用综合利用工序，其特征是：通过制浆废液的在线浓缩和高浓提取以及其后的蒸发浓缩、蒸发冷凝水回用和蒸发残液资源化利用实现制浆废液的零排放。制浆废液的在线浓缩和高浓提取，即在制浆过程中进行棉秆原料的色素分解——色素分离、逆向洗涤和前端提取。
进一步地，优选的工序流程为：原料洗涤(a)——原料蒸煮(b)——挤压(c1)——洗浆(d1)——搓丝(e1)——加药(f1)——浸渍(g1)——洗浆(h1)——高浓磨浆(i1)——加药(j1)——浸渍(漂白)(k1)——洗浆(l1)——高浓磨浆(m1)——洗浆(n1)。
进一步地：挤压(c1)——洗浆(d1)——搓丝(e1)——加药(f1)四道工序是在一台搓丝机上完成，优选的工序流程为：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef2)——浸渍(g2)——洗浆(h2)——高浓磨浆(i2)——加药(j2)——浸渍(漂白)(k2)——洗浆(l2)——高浓磨浆(n2)——洗浆(o2)。
进一步地：在洗浆(h2)环节后增加挤压洗浆搓丝加药(cdef3)——浸渍(g3)——洗浆(h3)环节，优选的工艺流程为：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef3)——浸渍(g3)——洗浆(h3)——挤压洗浆搓丝加药(i3)——浸渍(j3)——洗浆(k3)——高浓磨浆(l3)——加药(m3)——浸渍(漂白)(n3)——洗浆(o3)——高浓磨浆(p3)——洗浆如(q3)。
进一步地：色素分解——色素提取是在原料蒸煮(b)——挤压洗浆搓丝加药(cdef3)环节、浸渍(g3)——洗浆(h3)到挤压洗浆搓丝加药(i3)环节、浸渍(j3)——洗浆(k3)环节上完成。即在原料蒸煮(b3)环节上完成 色素分解，在挤压洗浆挤浆搓丝加药(cdef3)环节上通过废液提取完成色素提取；进而在浸渍(g3)环节上进一步完成色素分解，在洗浆(h3)环节上通过废液提取、随后在挤压洗浆搓丝加药(i3)环节完成挤压和洗浆并通过废液提取进一步完成色素提取；进一步在浸渍(j3)环节上完成色素分解，在洗浆(k3)环节上通过废液提取进一步完成色素提取。
进一步地：逆向洗涤是通过洗浆(q3)——加药(m3)和洗浆(o3)环节上完成，进一步通过洗浆(o3)——挤压洗浆搓丝加药(cdef3)和洗浆(k3)环节上完成。即用清水完成洗浆(q3)，洗浆(q3)产生的废液用于加药(m3)的配药和洗浆(o3)；进而将挤浆洗浆(o3)产生的废液用于挤压洗浆搓丝加药(i3)的加药和洗浆(k3)。
进一步地：前端提取是在挤压洗浆挤浆搓丝加药(cdef3)、洗浆(h3)环节和挤压洗浆搓丝加药(i3)、洗浆(k3)环节提取制浆废液。
进一步地：在浸渍(g2)环节后增加挤压洗浆挤浆搓丝加药(h4)——浸渍(i4)，优选的工艺流程为：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef4)——浸渍(g4)——挤压洗浆搓丝加药(h4)——浸渍(i4)——洗浆(j4)——高浓磨浆(k4)——加药(l4)——浸渍(漂白)(m4)——洗浆(n4)——高浓磨浆(o4)——洗浆(p4)。
进一步地：色素分解——色素提取是在原料蒸煮(b4)——挤压洗浆搓丝加药(cdef4)环节、浸渍(g4)——挤压洗浆搓丝加药(h4)环节、浸渍(i4)——洗浆(j4)环节上完成。即在原料蒸煮(b4)环节上完成色素分解，在挤压洗浆挤浆搓丝加药(cdef4)环节上通过废液提取完成色素提取；进而在浸渍(g4)环节上进一步完成色素分解，在挤压洗浆搓丝加药(h4)环节完成挤压和洗浆并通过废液提取进一步完成色素提取；进一步在浸渍(i4)环节上完成色素分解，在洗浆(j4)环节上通过废液提取进一步完成色素提取。
进一步地：逆向洗涤是通过洗浆(p4)——加药(l4)和洗浆(n4)环节上完成，进而通过洗浆(n4)——挤压洗浆搓丝加药(h4)和洗浆(j4)环节上完成。即用清水完成洗浆(p4)，洗浆(p4)产生的废液用于加药(l4)的 配药和洗浆(n4)；进而将挤浆洗浆(n4)产生的废液用于挤压洗浆搓丝加药(h4)的加药和洗浆(j4)。
进一步地：前端提取是在挤压洗浆搓丝加药(cdef4)、挤压洗浆搓丝加药(h4)和洗浆(j4)环节提取制浆废液。
进一步地：原料洗涤(1)工艺是通过洗涤脱除原料中的泥沙，原料浓度5％。用回用冷凝水补充原料洗涤工序(a)。
进一步地：原料蒸煮(b)工艺是通过连续或间歇式蒸煮器初步进行棉秆原料的色素分解。蒸煮工艺条件为：温度60～120min，药剂：碱性氧化物1～4％，使药液充分浸透棉秆原料达到饱和浆浓25～30％。用回用冷凝水补充原料蒸煮工序(b)。
进一步地：挤压洗浆搓丝加药(cdef2)环节是在同一台搓丝机上顺序完成挤压、洗浆、搓丝、加药四道工序。在搓丝机上专门开有洗浆液注入孔和废液排出口。药剂用量：双氧水4～6％(100％纯度)、碱性氧化物(100％纯度)2～5％原料重量百分比，稳定剂2～4％，螯合剂0.3～0.5％，MgSO40.05％,，浆浓20～30％，用回用冷凝水和逆向洗涤回用水补充完成洗浆和药剂稀释。
进一步地：浸渍，整个工艺流程中的给每一个浸渍环节均是同时完成漂白、纤维软化和完成粗浆色素分解以及一般污染污的分解。浸渍是在反应仓中保温条件下进行的，工艺条件为：温度60～95℃，保温60～150min。
进一步地：洗浆，整个工艺流程中的给每一个浸渍环节均是通过洗浆提取污水完成色素提取和一般污染物提取，并根据工艺要求控制浆浓。洗浆在挤浆机上完成，进将浓度8～25％,出浆浓度30～55％。用回用冷凝水和逆向洗涤回用水补充洗浆。
进一步地：二次挤压洗浆搓丝加药药剂用量：双氧水4～6％(100％纯度)、碱性氧化物(100％纯度)2～5％原料重量百分比，稳定剂2～4％，螯合剂 0.5～1％，MgSO40.05％,，浆浓20～30％，用回用冷凝水和逆向洗涤回用水补充完成洗浆和药剂稀释。
进一步地：蒸发浓缩是在多效蒸发站完成，是对在线前端提取的高浓制浆废液进行进一步浓缩，分离出冷凝水和蒸发残液分别回用于制浆和综合利用。
进一步地：冷凝水回用，即冷凝水从多效蒸发站流出，全部回用于原料洗涤、原料蒸煮和漂白加药环节。冷凝水分为清冷凝水和浊冷凝水，水温60℃以上，清冷凝水COD一般在400～600mg/L，COD900～1200mg/L。
进一步地：冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、洗浆(d1)、加药(f1)、洗浆(h1)环节。
进一步地：冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、挤压洗浆搓丝加药(cdef2)、洗浆(h2)环节。
进一步地：冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、挤压洗浆搓丝加药(cdef3)、洗浆(h3)、挤压洗浆搓丝加药(i3)、洗浆(k3)环节。
进一步地：冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、挤压洗浆搓丝加药(cdef4)、挤压洗浆搓丝加药(i4)、洗浆(k4)环节。
进一步地：用蒸发残液进行资源化利用，包括用蒸发残液生产肥料、碱木素或碱回收。
进一步地：生产肥料时，选用KOH作为碱性氧化物，并采用无钠稳定剂。
本发明的有益效果为：
1、通过化机浆制浆废液的前端高浓提取，有效减少对后续工序的污染负荷，有效提高全棉秸秆漂白化机浆的漂白效率。
2、化机浆制浆废水浓度高水量小，便于对制浆污水进行蒸发浓缩；
3、蒸发冷凝水全部循环回用于原料洗涤、原料蒸煮、原料浸渍漂白。
4、制浆废液得到资源化利用，从而实现化机浆制浆废液的零排放。
附图说明
图1本发明工艺流程图
具体的实施方式
实施例1
原料：全棉秸秆，产地：山东省聊城地区
备料：整秆原料风干，含水率14％，切断粉碎至20～50mm
中试平台：山东凯隆纸业科技有限公司1万吨/年高白度非木纤维漂白化机浆中试线
实施步骤：
采用的工艺流程为：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef4)——浸渍(g4)——挤压洗浆搓丝加药(h4)——浸渍(i4)——洗浆(j4)——高浓磨浆(k4)——加药(l4)——浸渍(漂白)(m4)——洗浆(n4)——高浓磨浆(o4)——洗浆(p4)。
1、原料洗涤(a)。在产量为1万吨/年鼓式原料洗涤器中进行，原料浓度5％，用COD在1100mg/L的回用的混合蒸发冷凝水补充原料洗涤用水。棉秆原料储存状态的含水率为14％，洗涤结束后含水率60％，在原料洗涤环节，除了排除泥沙带出很少量的水份，只有水分的补充，没有废水外排。水分的补充主要来自与山东凯隆纸业科技有限公司隔壁的山东泉林纸业有限责任公司的七效蒸发站的蒸发冷凝水。
2、原料蒸煮(b)。原料蒸煮是在保证原料充分吸收药液的条件下进行的。工艺条件为：温度为95℃，时间为60min，NaOH(100％纯度)2％，用量为原料重量百分比。蒸煮前原料含水率60％，蒸煮结束含水率30％，用回用的COD在1100mg/L污冷凝水补充水分，无废水外排。蒸煮补充水来自蒸发冷凝水。
3、挤压洗浆机浆搓丝加药(cdef4)。在搓丝机上顺序实现挤压洗浆挤浆搓丝加药。经过搓丝机的挤压段对原料进行挤压疏解的过程中挤出制浆废水，然后 原料进入洗浆挤浆段，注入蒸发冷凝水完成洗浆挤浆，产生的废水与挤压段排出的废水混合从搓丝机排出，作为前端提取的制浆废水收集去蒸发浓缩处理。从挤压洗浆机浆搓丝加药(cdef3)提取的废水COD：47321mg/L。
搓丝疏解后进行加药，加入药剂和回用的污冷凝水。药剂加入量为：双氧水(100％纯度)4％、药剂用量：NaOH(100％纯度)4％，Na2SiO34％，TDPA0.3％，渗透剂0.3％，MgSO40.01％，药剂用量均为原料重量百分比，浆浓25％。
4、浸渍(g3)。条件为：在1#漂白反应仓内95℃保温，时间120min。
5、挤压挤浆洗浆搓丝加药(h4)。在搓丝机上顺序实现二段挤压挤浆洗浆搓丝加药。然后原料进入洗浆机浆段，注入经过逆向洗涤从挤浆洗浆(o4)排出的废液完成洗浆挤浆，产生的废水与挤压段排除的废水废水混合从挤浆机排出，作为前端提取的制浆废水收集去蒸发浓缩处理。从挤压洗浆机浆搓丝加药(h4)提取的废水COD：32130mg/L。
搓丝疏解后进行加药，加入药剂和经过逆向洗涤从挤浆洗浆(o4)排出的废液。药剂加入量为：双氧水(100％纯度)6％、药剂用量：NaOH(100％纯度)4％，Na2SiO34％，TDPA0.05％，渗透剂0.05％，MgSO40.01％，药剂用量均为原料重量百分比，浆浓25％。
6、浸渍(i4)条件：条件为：在2#漂白反应仓内95℃保温，时间120min。
7、洗浆(j4)。在挤浆机内完成。进口浆浓20％，出口浆浓40％,补充挤浆用水来源于逆向洗涤从洗浆(o4)产生的废液。洗浆(j4)产生的废水作为前端提取收集后进行蒸发浓缩处理。洗浆(j4)提取的废水COD：54732mg/L。
8、高浓磨浆(k4)。磨浆浓度35％。
9、加药(l4)。在高浓磨浆机出口加入混合的药剂和来源于逆向洗涤从挤浆洗浆(p4)排出的洗浆废液作为药剂稀释水，浆浓30％，药剂加入量：双氧水(折纯2％)，NaHO1％，Na2SiO31％，DTPA0.2％，MgSO40.01％。
10、浸渍(漂白)(m4)。条件为：在3#漂白反应仓内95℃保温，时间120min。
11、洗浆(n4)。进口浆浓12％，出口浆浓35％，洗浆水来源于洗浆(p4)，挤浆废液用于挤压洗浆搓丝加药(h4)稀释水和洗浆(j4)。
12、高浓磨浆(o4)。磨浆浓度35％。
13、挤浆洗浆(p4)。进口浆浓20％，出口浆浓30％。挤浆洗浆用清水，产生的废水用于加药(l4)和洗浆(n4)。
14、制浆废水的混合。将挤压洗浆搓丝加药(cdef4)、挤压洗浆搓丝加药(h4)、洗浆(j4)提取的废液混合，得到在线浓缩后的废液，COD47228mg/L，固形物含量5.2％。
15、制浆废液的蒸发浓缩。即对经在线浓缩后的废液送入山东泉林纸业集团有限公司日处理1500段的七效蒸发站浓缩。过在线浓缩后的制浆废液进行多效蒸发进一步浓缩。
16、蒸发冷凝水的回用。蒸发污冷凝水和清冷凝水混合液小液COD1100mg/L，完全可以满足原料洗涤和原料蒸煮的要求。
17、制浆废液的资源化利用。由山东泉林纸业有限责任公司对制浆废液蒸发浓缩后的残渣用于肥料原料或燃料。
测试结果一：
纸浆指标测试：
全棉秸秆漂白化学机械浆检测报告
Figure PCTCN2015079084-appb-000001
Figure PCTCN2015079084-appb-000002
测试结果二：
蒸发残渣肥料成分：
成分 有机物含量 氮含量 磷含量 钾含量
数值 31.38％ 0.5％ 0％ 0％
实施例2
原料蒸煮(b)的工艺条件为：温度为40℃，时间为120min，NaOH2％。
实施例3
原料蒸煮(b)的工艺条件为：温度为99℃，时间为120min，NaOH1％。
实施例4
挤压挤浆洗浆搓丝加药(cdef4)的工艺条件为：双氧水5％、药剂用量：碱性氧化物(100％纯度)4％原料重量百分比，Na2SiO34％，DTPA0.3％，MgSO40.05％，浆浓25％。
实施例5
挤压挤浆洗浆搓丝加药(cdef4)的工艺条件为：双氧水7％、药剂用量：碱性氧化物(100％纯度)4％原料重量百分比，Na2SiO34％，DTPA0.3％，MgSO40.05％，浆浓25％。
实施例6
挤压挤浆洗浆搓丝加药(h4)的加药工艺条件为：双氧水4％、药剂用量：碱性氧化物(100％纯度)4％原料重量百分比，Na2SiO34％，DTPA0.3％，MgSO40.05％，浆浓25％。
实施例7
挤压挤浆洗浆搓丝加药(h4)的加药工艺条件为：双氧水5％、药剂用量：碱性氧化物(100％纯度)4％原料重量百分比，Na2SiO34％，DTPA0.2％，MgSO40.05％，浆浓25％。
实施例8
挤压挤浆洗浆搓丝加药(h4)的工艺条件为：双氧水7％、药剂用量：碱性氧化物(100％纯度)4％原料重量百分比，Na2SiO34％，DTPA0.2％，MgSO40.05％，浆浓25％。
实施例9
加药(l4)的工艺条件为：双氧水(100％纯度)3％、药剂用量：碱性氧化物(100％纯度)1％原料重量百分比，Na2SiO31％，DTPA0.1％，MgSO40.01％,，浆浓25％。
实施例10
加药(i)的工艺条件为：双氧水(100％纯度)4％、药剂用量：碱性氧化物(100％纯度)1.5％原料重量百分比，Na2SiO31％，DTPA0.1％，MgSO40.01％,，浆浓25％。
实例11
采取的工艺流程为：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef3)——浸渍(g3)——洗浆(h3)——挤压洗浆搓丝加药(i3)——浸渍(j3)——洗浆(k3)——高浓磨浆(l3)——加药(m3)——浸渍(漂白)(n3)——洗浆(o3)——高浓磨浆(p3)——洗浆如(q3)。洗浆(h3)的工艺条件为：洗浆挤浆在单螺旋机浆机上完成，进口浆浓20％，出口浆浓42％。其余各环节的工艺参数同实例1。
实施例2～11所制备的纸浆白度大于80％ISR，尘埃度：≤0.3cm2时，小于550个/m2；0.3～1.0cm2时，小于18个/m2，其他各项物性指标能够满足印刷用纸的生产要求。
上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。

Claims (28)

  1. 一种全棉秸秆化机浆制浆废液的零排放工艺，包括制浆漂白工序和制浆漂白废水回用及零排放工序，其特征是：通过制浆废液的前端提取以及其后的蒸发浓缩、蒸发冷凝水回用和蒸发残液的资源化利用实现制浆废液的零排放。
    在线浓缩和高浓提取，即在制浆过程中进行棉秆原料的色素分解——色素分离、逆向洗涤和前端提取。色素分解即棉秆色素与棉秆原料或棉杆纤维的分离，色素提取将棉秆色素从棉秆纤维中提取并以制浆废液的形式排出。
  2. 如权利要求1所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述制浆漂白工序包括：原料洗涤(a)——原料蒸煮(b)——挤压(c1)——洗浆(d1)——搓丝(e1)——加药(f1)——浸渍(g1)——洗浆(h1)——高浓磨浆(i1)——加药(j1)——浸渍(漂白)(k1)——洗浆(l1)——高浓磨浆(m1)——洗浆(n1)。
  3. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：挤压(c1)——洗浆(d1)——搓丝(e1)——加药(f1)四道工序是在一台搓丝机上完成。
  4. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述制浆漂白工序包括：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef2)——浸渍(g2)——洗浆(h2)——高浓磨浆(i2)——加药(j2)——浸渍(漂白)(k2)——洗浆(l2)——高浓磨浆(n2)——洗浆(o2)。
  5. 如权利要求4所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：在洗浆(h2)环节后增加挤压洗浆搓丝加药(i3)——浸渍(j3)——洗浆(k3)环节。
  6. 如权利要求5所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述制浆漂白工序包括：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef3)——浸渍(g3)——洗浆(h3)——挤压洗浆搓丝加药(i3)——浸渍(j3)——洗浆(k3)——高浓磨浆(l3)——加药(m3)——浸渍(漂白)(n3)——洗浆(o3)——高浓磨浆(p3)——洗浆(q3)。
  7. 权利要求6所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述棉秆原料的色素分解——色素分离是在原料蒸煮(b)——挤压洗浆搓丝加药(cdef3)环节、浸渍(g3)——洗浆(h3)到挤压洗浆搓丝加药(i3)环节和浸渍(j3)——洗浆(k3)环节上完成。
  8. 如权利要求6所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：逆向洗涤是通过洗浆(q3)——加药(m3)和洗浆(o3)环节上完成，进一步通过洗浆(o3)——挤压洗浆搓丝加药(i3)和洗浆(k3)环节上完成。
  9. 如权利要求6所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：前端提取是在挤压洗浆挤浆搓丝加药(cdef3)、洗浆(h3)环节和挤压洗浆搓丝加药(i3)、洗浆(k3)环节提取制浆废液。
  10. 如权利要求4所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：在浸渍(g2)环节后增加挤压洗浆挤浆搓丝加药(h4)——浸渍(i4)。
  11. 如权利要求10所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述制浆漂白工序包括：原料洗涤(a)——原料蒸煮(b)——挤压洗浆搓丝加药(cdef4)——浸渍(g4)——挤压洗浆搓丝加药(h4)——浸渍(i4)——洗浆(j4)——高浓磨浆(k4)——加药(l4)——浸渍(漂白)(m4)——洗浆(n4)——高浓磨浆(o4)——洗浆(p4)。
  12. 权利要求11所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述棉秆原料的色素分解——色素分离是在原料蒸煮(b)——挤压洗浆搓丝加药(cdef4)环节和浸渍(g4)——挤压洗浆搓丝加药(h4)环节以及浸渍(i4)——洗浆(j4)环节上完成。
  13. 如权利要求11所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：逆向洗涤是通过洗浆(p4)——加药(l4)和洗浆(n4)环节上完成，进而通过洗浆(n4)——挤压洗浆搓丝加药(h4)和洗浆(j4)环节上完成。即用清水完成洗浆(p4)，洗浆(p4)产生的废液用于加药(l4)的配药和洗 浆(n4)；进而将挤浆洗浆(n4)产生的废液用于挤压洗浆搓丝加药(h4)的加药和洗浆(j4)。
  14. 如权利要求11所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：前端提取是在挤压洗浆搓丝加药(cdef4)、挤压洗浆搓丝加药(h4)和洗浆(j4)环节提取制浆废液。
  15. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：原料洗涤(1)工艺是通过洗涤脱除原料中的泥沙，原料浓度5％。用回用冷凝水补充原料洗涤工序(a)。
  16. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：原料蒸煮(b)工艺是通过连续或间歇式蒸煮器初步进行棉秆原料的色素分解。蒸煮工艺条件为：温度60～120min，药剂：碱性氧化物用量为占原料重量的百分比为1～3％，使药液充分浸透棉秆原料达到饱和浆浓25～30％；用回用冷凝水补充原料蒸煮工序(b)。
  17. 如权利要求3所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：挤压洗浆搓丝加药环节是在同一台搓丝机上顺序完成挤压、洗浆、搓丝、加药四道工序。在搓丝机上专门开有洗浆液注入孔和废液排出口。药剂用量占原料重量的百分比如下：双氧水4～6％、碱性氧化物2～5％，稳定剂2～4％，螯合剂0.3～0.5％，MgSO4 0.05％,，浆浓20～30％，用回用冷凝水和逆向洗涤回用水补充完成洗浆和药剂稀释。
  18. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：浸渍，整个工艺流程中的给每一个浸渍环节均是同时完成漂白、纤维软化和完成粗浆色素分解以及一般污染污的分解；浸渍是在反应仓中保温条件下进行的，工艺条件为：温度60～95℃，保温60～150min。
  19. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：洗浆，整个工艺流程中的每一个洗浆环节均是通过洗浆提取污水完成色 素提取，并根据工艺要求控制浆浓。洗浆在挤浆机上完成，进口将浓度8～25％,出浆浓度30～55％；用回用冷凝水和逆向洗涤回用水补充洗浆。
  20. 如权利要求3所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：二次挤压洗浆搓丝加药；药剂用量占原料重量的百分比如下：双氧水4～6％、碱性氧化物2～5％，稳定剂2～4％，螯合剂0.2～0.3％，MgSO4 0.05％,，浆浓20～30％，用回用冷凝水和逆向洗涤回用水补充完成洗浆和药剂稀释。
  21. 如权利要求1所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：蒸发浓缩是在多效蒸发站完成，是对在线前端提取的高浓制浆废液进行进一步蒸发浓缩。通过蒸发浓缩分离出冷凝水和蒸发残液，分别回用于制浆和资源化利用。
  22. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述工序中还包括冷凝水回用环节，即冷凝水从多效蒸发站流出，全部回用于原料洗涤、原料蒸煮和漂白加药环节；冷凝水分为清冷凝水和浊冷凝水，水温60℃以上，清冷凝水COD在400～600mg/L，COD900～1200mg/L。
  23. 如权利要求2所述一种全棉秸秆化机浆制浆废液的零排放工艺，特征是：所述工序中还包括冷凝水回用环节，冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、洗浆(d1)、加药(f1)、洗浆(h1)环节。
  24. 如权利要求3所述一种全棉秸秆化机浆制浆废液的零排放工艺，特征是：所述工序中还包括冷凝水回用环节，冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、挤压洗浆搓丝加药(cdef2)、洗浆(h2)环节。
  25. 如权利要求4所述一种全棉秸秆化机浆制浆废液的零排放工艺，特征是：所述工序中还包括冷凝水回用环节，冷凝水回用去向为：原料洗涤(a)、原料蒸煮(b)、挤压洗浆搓丝加药(cdef3)、洗浆(h3)、挤压洗浆搓丝加药(i3)、洗浆(k3)环节。
  26. 如权利要求11所述一种全棉秸秆化机浆制浆废液的零排放工艺，特征是：所述工序中还包括冷凝水回用环节，冷凝水回用去向为：原料洗涤(a)、 原料蒸煮(b)、挤压洗浆搓丝加药(cdef4)、挤压洗浆搓丝加药(h4)、洗浆(j4)环节。
  27. 如权利要求1所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：所述蒸发残液的资源化利用，包括用蒸发残液生产肥料或碱回收。
  28. 如权利要求26所述一种全棉秸秆化机浆制浆废液的零排放工艺，其特征是：生产肥料时，选用KOH作为碱性氧化物，并采用无钠稳定剂。
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