CN100420790C - Alkali process and iminium process straw pulp black liquor hybrid dry matter and preparation method thereof - Google Patents
Alkali process and iminium process straw pulp black liquor hybrid dry matter and preparation method thereof Download PDFInfo
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- CN100420790C CN100420790C CNB2007101654474A CN200710165447A CN100420790C CN 100420790 C CN100420790 C CN 100420790C CN B2007101654474 A CNB2007101654474 A CN B2007101654474A CN 200710165447 A CN200710165447 A CN 200710165447A CN 100420790 C CN100420790 C CN 100420790C
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- 238000000034 method Methods 0.000 title claims abstract description 220
- 239000010902 straw Substances 0.000 title claims abstract description 189
- 239000003513 alkali Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims description 89
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 128
- 238000001704 evaporation Methods 0.000 claims abstract description 100
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- 238000002156 mixing Methods 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 22
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims abstract description 21
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 230000008020 evaporation Effects 0.000 claims description 97
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- 238000009833 condensation Methods 0.000 abstract 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a mixture of dried grain of alkali and ammonium sulfite black straw liquor as well as relevant preparation method. The invention is mainly a product by mixing alkali method black straw liquor with ammonium sulfite black straw liquor before performing condensation and drying, as well as relevant products that are produced. Evaporating and condensing black liquor with the production technique needs less energy consumption, and main dried grains include sodium lignin and ammonium lignin sulfonate as well as fulvic acid like substances. Therefore, the invention has broad application and can be used as raw materials for many products with high economic value. Moreover, the invention can also be utilized in preparation of an excellent water reducer, or be added with some crosslinkers to prepare lignin sand-fixing solvent.
Description
Technical field
The present invention relates to the treatment technology of straw pulp black liquor, mainly is to carry out the technology of concentrate drying and the dry thing of acquisition thereof after alkaline straw-pulp black liquid and the straw pulp black liquor by ammonium sulfite method mixing.
Background technology
More than 80% grass fiber in China's paper industry raw material.Grass fiber papermaking mainly contains two kinds, soda pulping process and sulfite pulping, in the sulphite process again based on Ammonium Sulfite Method.Soda pulping process is to utilize the aqueous solution of alkali electroless medicament to handle plant fiber material, and with the lignin stripping in the raw material, make fiber from wherein being separated into the method for paper pulp, pulping with ammonium sulfite method is with the lignin effect in ammonium sulfite and the plant fiber material, generate easily molten lignosulphonates and stripping, to reach the purpose of defibre.
After the soda pulping process, there are 50% fibrous raw material and most alkaline matter to be dissolved in the cooking liquor approximately, become black liquor, contain poly-pentose, lignin, sulfate soap and alkaloids in the black liquor waste, so waste water is black.CODcr generally about 100000～180000mg/L, pH value 10～13, CODcr surpasses more than 50 times of discharge standard, owing to the decolouring difficulty, enter water body and seriously consume dissolved oxygen, is difficult to handle with conventional method.
Pulping with ammonium sulfite method is same to produce a large amount of black liquor, and the composition of its black liquor also contains ammonium nitrogen, sugar and other is organic except ammonium lignin sulfonate.Its CODcr is generally more than 120000mg/L.
The external Silvola recovery that adopts is handled pulp black liquor more, but this method investment is big, and complex process equipment only is applicable to large-scale pulping wood papermaking enterprise.And aspect alkaline straw-pulp black liquid improvement, adopt alkali recovery technology, and require the slurrying scale minimum for producing 1.7 ten thousand tons per year, construction investment is big, the operating cost height.And straw pulp black liquor exists and is unfavorable for aptitude to burn: viscosity is big, and the activation energy of black liquor is very high, black liquor burning-point height, be difficult to burning, caloric value is low, the silicon content height, half fiber and heteroproteose cell are many and be easy to rotten and the generation precipitation, are difficult to apply at medium-sized straw pulp mill.Acidization and ultrafiltration are adopted in the domestic in recent years processing to medium-sized and small enterprises' black liquid more, mainly are to extract the lignin in the black liquor and reduce COD and BOD.But these methods all can not be eliminated the organic matter in the black liquor fully, and the shipwreck after the processing is to reach discharging standards.
And, can directly be used as fertilizer for straw pulp black liquor by ammonium sulfite method, draw to the field or by pipeline with the container accumulating and be poured into the field and directly apply fertilizer, but the byproduct discharge liquor in this paper mill, quantity is very big, and based on product form, is difficult to store.Because the direct as fertilizer sources of this discharge liquor, all multifactor restrictions such as amount of stored, season, field being born irrigation, consumption is very limited, major part has to discharge on the spot, the loss of giving free rein to, not only serious environmental pollution, but also caused the waste of resource such as nutrient and organic matter in the discharge liquor.
For nutrient and the organic matter that makes full use of straw pulp black liquor by ammonium sulfite method, can utilize it to produce fertilizer or manufacturing ammonium lignin sulfonate, as application number is the Chinese patent of CN01145263, utilize straw pulp black liquor by ammonium sulfite method to put forward dense back drying and obtain the solid material, again with the granulation of solid material or add other component and make compoiste fertilizer; Application number is the Chinese patent of CN98110161, will add after the straw pulp black liquor by ammonium sulfite method evaporation and concentration that trace element makes granular compound fertilizer; Application number is the Chinese patent of CN00124912, and earlier with the straw pulp black liquor by ammonium sulfite method filtration, purification, ammonium lignin sulfonate is made in low dense evaporation back spraying oven dry.
Above-mentioned patent all only relates to the utilization of single kind black liquor, but in fact, the pH of single kind black liquor does not often meet the utilization of industrial and agricultural production, the pH of alkaline straw-pulp black liquid is 9～13, the pH of straw pulp black liquor by ammonium sulfite method is 7-10, therefore often meta-acid or alkali partially need to add extra acid in actual production or alkali is regulated its pH value, have increased cost.The present invention mixes alkaline process and straw pulp black liquor by ammonium sulfite method, utilizes different mixed proportions to obtain needed pH, can significantly reduce cost.With obtaining alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter after the mixed straw pulp black liquor drying, can be used as a kind of outstanding fertilizer, the soil pH that the solid content of having avoided when being manured into soil forming after the single kind black liquor drying causes sharply changes.
Simultaneously, all relate to the evaporation and concentration of black liquor in the above-mentioned patent, but in actual production, because there is NH in straw pulp black liquor by ammonium sulfite method when evaporation and concentration
3Volatilization, can cause the rapid decline of black liquor pH, thereby can cause serious corrosion equipment, simultaneously, above-mentioned patent exists evaporation efficiency low in varying degrees, high shortcoming consumes energy.
Patent of the present invention has overcome above shortcoming, in straw pulp black liquor by ammonium sulfite method, add alkaline straw-pulp black liquid, its pH is raise, thereby improved the pH of black liquor in the evaporating concentration process, reduced corrosion, do not increased extra cost again, can handle two kinds of black liquor simultaneously equipment, and the inventor is through big quantity research, adopt multiple-effect evaporation, determined the optimal processing parameter of multiple-effect evaporation, added multistep flash distillation step, the heat utilization efficiency height, it is low to consume energy, and contain alkali lignin and ammonium lignin sulfonate and xanthohumic acid kind material in alkaline process that obtains and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, so it is of many uses, can be used as the raw material of multiple product, as can be used for preparing outstanding water reducer, and also can add little amount of crosslinking agent, be used to prepare the lignin sand-consolidating agent, can turn waste into wealth, obtain good economic worth.
Summary of the invention
The object of the present invention is to provide a kind of alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
Another object of the present invention is to provide the preparation method of above-mentioned alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing.
A kind of alkaline process provided by the invention and straw pulp black liquor by ammonium sulfite method hybrid dry matter, it is characterized in that, described alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter are after straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid mix, being dried to moisture weight percentage≤20% forms, the volume ratio of described straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1: 100-100: 1
Wherein alkali lignin content is that 0.1-90%, ammonium lignin sulfonate content are 0.1-60%, and fulvic acid content is 1-35%, and moisture is 0-20%.
Described straw pulp black liquor by ammonium sulfite method content of cellulose≤200mg/L, Baume degrees 2-9, solid content=4-15%, pH are 7-10; Described alkaline straw-pulp black liquid content of cellulose≤200mg/L, Baume degrees 2-9, solid content are 4-15%, pH is 9-13.The volume ratio of preferred straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1: 10-10: 1, more preferably 1: 4-4: 1, at this moment, alkali lignin content is that 20-70%, ammonium lignin sulfonate content are 15-40% in alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, fulvic acid content is 5-30%, and moisture is 0-10%.
The present invention also provides the preparation method of above-mentioned alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter, comprising:
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are mixed, obtain the mixed straw black liquor;
(2) evaporation and concentration
The mixed straw black liquor is carried out evaporation and concentration till moisture weight percentage≤20%, obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
The present invention also provides another efficient energy-saving preparation method of above-mentioned alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter, it is characterized in that, comprises
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are mixed, obtain the mixed straw black liquor;
(2) evaporation and concentration
It is 40-47% that the mixed straw black liquor is carried out evaporation and concentration to solid content, and Baume degrees is 25-29, obtains alkaline process and Ammonium Sulfite Method and mixes concentrated straw pulp black liquor;
(3) slurry-spraying pelletizing or spray drying
Alkaline process and Ammonium Sulfite Method are mixed concentrated straw pulp black liquor slurry-spraying pelletizing or be spray dried to solid content, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
Wherein, also comprise before described step (2) evaporation and concentration mixed straw black liquor is carried out flash distillation, preferably carry out 2 flash distillations continuously.
Described evaporation and concentration is a multiple-effect evaporation, and preferred five imitate evaporation.
Described five effect evaporation processes are countercurrent multi-effect evaporation, mixed straw black liquor after the flash distillation is imitated from V and is flowed into, heating steam is imitated from I and is flowed into, mixed straw black liquor after the flash distillation is imitated, after IV is imitated, III imitates heating evaporation, is become low half concentrated black liquid through V successively, low half concentrated black liquid successively through II imitate, after I imitates heating evaporation, become half concentrated black liquid, half concentrated black liquid is imitated through II successively again and I is imitated heating evaporation, becomes concentrated black liquid, is alkaline process and Ammonium Sulfite Method and mixes concentrated straw pulp black liquor.
Described five effect evaporations are respectively imitated pressure and are: I is imitated 20-38kPa, II effect-19～0kPa, III effect-58～-40kPa, IV effect-73～-60kPa, V effect-84～-79kPa;
Each imitates black liquor temperature:
100-120 ℃ of I effect, 90-100 ℃ of II effect, 80-90 ℃ of III effect, 70-80 ℃ of IV effect, V are imitated 57-65 ℃
Each is imitated black liquid wave hairdressing and is respectively:
V is imitated 5-9, IV and is imitated 9-12, III effect 11-14; During for the first time through II effect and I effect, II is imitated 14-17, I and is imitated 18-21; During for the second time through II effect and I effect, II is imitated 23-25, I and is imitated 27-29.
Described low half concentrated black liquid solid content is 20-25%, and Baume degrees is 11-14; Described half concentrated black liquid solid content is 30-35%, and Baume degrees is 18-21.
Described heating steam temperature is 140 ℃, and pressure is 0.2-0.4MPa, becomes the cleaning condensed water through heat exchange after I is imitated inflow, temperature is 105 ℃-120 ℃, described cleaning condensed water carries out flash distillation again, and the steam that flashes off utilizes once more, to improve the heat energy utilization rate.
Inlet temperature is 360-400 ℃ during described spray drying, outlet temperature 85-130 ℃; Slurry-spraying pelletizing machine head temperature is 550～600 ℃ during described slurry-spraying pelletizing, 47-55 ℃ of tail temperature, returning charge amount 〉=50%.
Below the present invention is launched to describe in detail:
Why the present invention obtains alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter with alkaline process and straw pulp black liquor by ammonium sulfite method combination drying, be because the pH of single kind black liquor does not often meet the utilization of industrial and agricultural production, the pH of alkaline straw-pulp black liquid is 9～13, the pH of straw pulp black liquor by ammonium sulfite method is 7-10, often meta-acid or alkali partially, therefore in actual production, evaporation and concentration meeting etching apparatus, during the solid content that forms after the single kind black liquor drying is manured into soil, tend to cause the rapid variation of soil pH, regulate its pH value so need to add extra acid or alkali, increased cost.
The present invention mixes alkaline process and straw pulp black liquor by ammonium sulfite method, utilizes different mixed proportions to obtain needed pH, can significantly reduce cost.Wherein, the volume ratio of straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid can be 1: 100-100: 1, be dried to percent water content and be lower than at 20% o'clock, alkali lignin content is that 0.1-90%, ammonium lignin sulfonate content are 0.1-60% in alkaline process that obtains and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, fulvic acid content is 1-35%, and moisture is 0-20%.The volume ratio of preferred straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1: 10-10: 1, more preferably 1: 4-4: 1, at this moment, the mixed straw black liquor that forms when pH descends when follow-up evaporation and concentration the corrosion to equipment be unlikely to too big, make the nutrient content of mixed straw black liquor when making fertilizer at reasonable range (this be because Ammonium Sulfite Method black liquor generally than the nutrient content height of alkaline process black liquor) again, after the drying, alkali lignin content is 20-70% in alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, ammonium lignin sulfonate content is 15-40%, and fulvic acid content is 5-30%.
Alkali lignin derives from alkaline straw-pulp black liquid in the said components, ammonium lignin sulfonate derives from straw pulp black liquor by ammonium sulfite method, fulvic acid is the common component of two kinds of straw pulp black liquors, this is owing to have more fulvic acid in the black liquid, wherein the content in the straw pulp black liquor by ammonium sulfite method surpasses 10%, and alkaline straw-pulp black liquid content is lower slightly.Since natural fulvic acid by plant residue under the condition that air and moisture content exist, experienced very long natural process, through partly decomposing and forming. by investigation and analysis, fulvic acid in the straw pulp black liquor is because in the pulping process, at high temperature, add and depress cooking plant fiber, be equivalent to quicken original natural process, except main generation supplies the paper pulp fiber of paper grade (stock), also generated a considerable number of fulvic acid.
The present invention also provides the preparation method of above-mentioned alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter, comprising:
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are mixed, obtain the mixed straw black liquor;
(2) evaporation and concentration
The mixed straw black liquor is carried out evaporation and concentration till moisture weight percentage≤20%, obtain till alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter.
But, directly black liquor vaporizing is concentrated into and obtains solid content, exist evaporation efficiency low; high shortcoming consumes energy; therefore, the invention provides another energy-efficient preparation method, at first mixed straw pulp black liquor being adopted evaporation and concentration is 40-47% to solid content; Baume degrees is 25-29; dry then, further, evaporation and concentration adopts multiple-effect evaporation; dry slurry-spraying pelletizing or the spray drying of adopting, specific as follows described:
(1) mixes
At first, alkaline straw-pulp black liquid and straw pulp black liquor by ammonium sulfite method are mixed, before mixing, must be from the straw pulp by neutral ammonium sulfite process of press master rare black liquor and the rare black liquor of alkaline straw-pulp filter respectively, to remove cellulose wherein, prevent from subsequent technique is had a negative impact.The step of filter fiber is used fibre filter, through the straw pulp black liquor by ammonium sulfite method content of cellulose≤200mg/L behind the fibre filter, Baume degrees 2-9, solid content=4-15%, pH7-10, temperature=60-80 ℃; Alkaline straw-pulp black liquid content of cellulose (crossing 325 mesh sieve)≤200mg/L, Baume degrees 2-9, solid content=4-15%, pH=9-13, temperature=60-80 ℃.
The straw pulp black liquor by ammonium sulfite method of removing fiber is mixed in proportion with alkaline straw-pulp black liquid, most preferably volume ratio is 1: 4-4: 1, and mixed straw pulp black liquor content of cellulose (crossing 325 mesh sieve)≤200mg/L, Baume degrees 2-9 or solid content=4-15%, pH=5-11, temperature=60-80 ℃.
Why straw pulp black liquor by ammonium sulfite method will be mixed with alkaline straw-pulp black liquid, be because there is NH in straw pulp black liquor by ammonium sulfite method when evaporation and concentration
3Volatilization, can cause the rapid decline of black liquor pH, thereby can cause serious corrosion equipment, therefore be necessary the pH of straw pulp black liquor by ammonium sulfite method is improved, and then improve the pH of black liquor in the evaporating concentration process, to reduce corrosion to equipment.The pH that improves straw pulp black liquor by ammonium sulfite method has several different methods, as can adding alkali such as NaOH, KOH, but can increase extra cost like this.So, the inventor takes to add alkaline straw-pulp black liquid, and the pH of alkaline straw-pulp black liquid is in general than the pH height of straw pulp black liquor by ammonium sulfite method, and the refuse that produces when being similarly slurrying of alkaline straw-pulp black liquid, be difficult to administer, use alkaline straw-pulp black liquid can play the purpose that the comprehensive regulation utilizes.
The mixed straw black liquor at first flows into rare black liquor groove, and rare black liquor groove plays storage tank.
(2) evaporation and concentration
In order to make full use of the heat of black liquor self, improve the heat energy utilization rate, reduce cost, the mixed straw black liquor can be carried out flash distillation before evaporation and concentration, preferably carry out 2 flash distillations continuously.Flash distillation makes the mixed straw black liquor produce small amount of steam, and the III after the steam of 2 flash tanks feeds respectively in the step is imitated and the IV single-effect evaporator, can utilize the heat of mixed straw black liquor self,
The temperature that the mixed straw black liquor flows into flash tank is 60-80 ℃, and after 2 step flash distillations, variations in temperature is little, and solid content does not have significant change, then evaporation and concentration.
The mixed straw black liquor is carried out evaporation and concentration, preferred multiple-effect evaporation, I is imitated and is added heating steam in the multiple-effect evaporation, the indirect steam temperature that wherein steams is lower than heating steam, can be used as that II imitates heating steam, II is imitated the heating steam that the indirect steam that steams is imitated as III, and the like, the heating steam temperature that each is imitated and the operating pressure of each effect reduce successively, and each boiling temperature of imitating solution also reduces successively.
Along with the increase of imitating number, the unit steam consumption reduces gradually, considers but come from running cost, and evaporation is imitated in the present invention preferred five, and used equipment is quintuple effect evaporator.Be example with five efficient tubular falling film evaporators below, the technological parameter and the operation principle of each effect done detailed description:
In the quintuple effect evaporator each is imitated and is divided into three parts usually, topmost is a distribution plate, effect is that black liquor mean allocation that circulating pump is drawn up is in each pipe, the centre is an air chamber, be the heat exchange area of steam and black liquor, this regional evapotranspiration of black liquor concentrates, and foot is a liquid chamber, black liquor after the evaporation and concentration flows into this position, and concrete structure is seen Fig. 4.
Generally speaking, the material in the quintuple effect evaporator can be divided into gas phase and liquid phase two parts, and liquid phase is a black liquor, and gas phase is a steam, flows as follows respectively mutually:
1, liquid phase is that black liquor flows to: as shown in Figure 2.
2, gas phase is a steam flow: as shown in Figure 3.
The mixed straw black liquor flows into the V single-effect evaporator, is concentrated by the Steam Heating from the IV single-effect evaporator, enters the IV single-effect evaporator, concentrated by the Steam Heating of imitating, enter low half concentrated black liquid groove, become low half concentrated black liquid from III, solid content is 20-25%, and Baume degrees is 11-14.
Low half concentrated black liquid enters II single-effect evaporator and I single-effect evaporator then successively, is heated by steam to enter half concentrated black liquid groove after concentrating, and becomes half concentrated black liquid, and solid content is 30-35%, and Baume degrees is 18-21.
Half concentrated black liquid enters the II effect again successively and I is imitated the black liquor groove, is heated by steam to concentrate promptly to become concentrated black liquid, flows into the concentrated black liquid groove.
Concentrated black liquid is that alkaline process and Ammonium Sulfite Method are mixed concentrated straw pulp black liquor, and its solid content is 40-47%, and Baume degrees is 25-29, pH=5-11.
In quintuple effect evaporator, gas phase is that the flow direction of steam is just opposite, and purpose is to increase the temperature difference between gas phase and liquid phase, improves heat exchanger effectiveness.Wherein, the initial vapor (steam) temperature of coming out from steam generator is 200-210 ℃, pressure=0.8-1MPa, drop to 0.2-0.4MPa, about 140 ℃ through pressure-reducing valve, feeding I imitates, the steam of this moment is cleaning steam, after the black liquor of imitating with I carries out heat exchange, become the cleaning condensed water, the temperature of cleaning condensed water is 105 ℃-120 ℃, in order to make full use of its heat, it is passed through a flash tank, the steam of flash distillation feeds the II single-effect evaporator, and the cleaning condensed water of discharge can be used for the pulp washing of pulping process.
The steam of the black liquor vaporizing that I is imitated enters II and imitates, as the heating steam that II is imitated, same, the evaporated vapor that the steam of the black liquor vaporizing that II is imitated is imitated as III, and the like, the steam of II, III, IV, V black liquor vaporizing is dirty steam, because of it is that last effect boiling black liquor produces, after itself and this effect black liquor carries out heat exchange, promptly form foul condensate, the foul condensate that II, III, IV, V are imitated finally is summarised in together, and COD flows to sewage treatment plant and handles about 1500mg/L.
The temperature of black liquor is followed successively by in above-mentioned each effect:
100-120 ℃ of I effect, 90-100 ℃ of II effect, 80-90 ℃ of III effect, 70-80 ℃ of IV effect, V are imitated 57-65 ℃;
Each pressure of imitating is:
I effect 20-38kPa, II effect-19～0kPa, III effect-58～-40kPa, IV effect-73～-60kPa, V effect-84～-79kPa, all pressure all are relative pressure herein, relative atmospheric pressure.
Each is imitated black liquid wave hairdressing and is respectively:
V is imitated 5-9, IV and is imitated 9-12, III effect 11-14; During for the first time through II effect and I effect, II is imitated 14-17, I and is imitated 18-21; During for the second time through II effect and I effect, II is imitated 23-25, I and is imitated 27-29.
Each heat exchange area of imitating can be decided on the Design Treatment ability, with the Design Treatment ability: and 70 tons/h of evaporation water, handle 2000m every day
3Imonium and the mixing black liquor of alkali; Logical quantity of steam is 17.5 tons/h under the normal duty, and the heat exchange area of every effect is: I is imitated 1600m
2, II imitates 1200m
2, III imitates, IV is imitated, V is imitated all is 900m
2
Why above-mentioned black liquor wants 2 times by II effect and I single-effect evaporator, be because quintuple effect evaporator just is difficult to once rare black liquor vaporizing simmer down to half concentrated black liquid until concentrated black liquid, need to imitate through II for twice and the I single-effect evaporator just can meet the demands, mean intermittent production aborning.Therefore can further improve technology, increase the effect number of multi-effect evaporator, in general, six effects, seven evacuator body devices can satisfy a step and propose dense requirement.
In addition, in design,, often need N in each single-effect evaporator in order to improve heat exchanger effectiveness
2Remove Deng incoagulable gas, this can realize at air chamber and vacuum pipe junction restricting orifice being arranged by connect a vavuum pump at the air chamber place, only allow incoagulable gas to pass through, and steam can't pass through.
(3) drying
Alkaline process and the concentrated straw pulp black liquor of Ammonium Sulfite Method mixing are dried to solid content, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, drying means preferably spray drying or slurry-spraying pelletizing.During spray drying inlet temperature 360-400 ℃, outlet temperature 85-130 ℃; Slurry-spraying pelletizing machine head temperature is 550～600 ℃ during slurry-spraying pelletizing, 47-55 ℃ of tail temperature, and for carrying out continuously of guaranteeing to produce, the returning charge amount wants 〉=50%.
Alkaline process provided by the invention and Ammonium Sulfite Method hybrid dry matter can not rely on the adjusting that the acid that adds or alkali are realized pH, can industrial raw material, and also can be directly as outstanding fertilizer.Mainly contain alkali lignin and ammonium lignin sulfonate and xanthohumic acid kind material, therefore it is of many uses, can be used as multiple raw material with very high economic worth product, also can be used for preparing outstanding water reducer, also can add little amount of crosslinking agent, be used to prepare the lignin sand-consolidating agent, have good economic worth.Simultaneously, the alkaline process of generation and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing are solid, are convenient to store and transportation.
Adopt production technology evaporation and concentration black liquor of the present invention, have the following advantages:
1, can prevent straw pulp black liquor by ammonium sulfite method when evaporation and concentration because NH
3The rapid decline of the black liquor pH that causes of volatilization, the serious corrosion that equipment is caused;
2, energy resource consumption is few, and steam per ton can be taken away 4-6 ton moisture, and black liquor can be concentrated to the 40-43% non-scaling, and the foul condensate COD of generation is 1500mg/L only, be easy to administer,
Description of drawings
Fig. 1 the present invention adopts five to imitate evaporation technology concentrate drying product technology
Fig. 2 five is imitated liquid phase flow direction in the evaporation
Fig. 3 five is imitated gas phase flow direction in the evaporation
The brief configuration schematic diagram of Fig. 4 evaporimeter
The specific embodiment
Embodiment 1
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 1: 100 mixed of volume ratio, are obtained the mixed straw black liquor; Wherein the straw pulp black liquor by ammonium sulfite method Baume degrees 2, solid content=4%, pH=7; Described alkaline straw-pulp black liquid, Baume degrees 2, solid content=4%, pH=9; Mixed alkaline process and Ammonium Sulfite Method mixed straw black liquor, Baume degrees 2, solid content=4%, pH=8.7.
(2) evaporation and concentration
The mixed straw black liquor is carried out direct evaporation and concentration, till moisture weight percentage≤20%, obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
Alkali lignin content is 90% in described alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, ammonium lignin sulfonate content is 0.1, and fulvic acid content is 1, and moisture is 5%.
Embodiment 2
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 100: 1 mixed of volume ratio, are obtained the mixed straw black liquor; Straw pulp black liquor by ammonium sulfite method content of cellulose 200mg/L wherein, Baume degrees 9, solid content=15%, pH10; Described alkaline straw-pulp black liquid content of cellulose 200mg/L, Baume degrees 9, solid content=15%, pH=13; Mixed alkaline process and Ammonium Sulfite Method mixed straw black liquor, Baume degrees 9, solid content=15%, pH=9.3;
(2) evaporation and concentration
The mixed straw black liquor is carried out direct evaporation and concentration, till moisture weight percentage≤20%, obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
Alkali lignin content is 0.1% in described alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, ammonium lignin sulfonate content is 60%, and fulvic acid content is 35%, and moisture is 3%.
Embodiment 3
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 70: 30 mixed of volume ratio, are obtained the mixed straw black liquor; Straw pulp black liquor by ammonium sulfite method content of cellulose 100mg/L wherein, Baume degrees 7, solid content=10%, pH8; Described alkaline straw-pulp black liquid content of cellulose 100mg/L, Baume degrees 7, solid content=10%, pH=10; Mixed alkaline process and Ammonium Sulfite Method mixed straw black liquor, Baume degrees 7, solid content=10%, pH=9.1;
(2) evaporation and concentration
The mixed straw black liquor is carried out direct evaporation and concentration, till moisture weight percentage≤20%, obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
Alkali lignin content is 12.2% in described alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, ammonium lignin sulfonate content is 48.7%, and fulvic acid content is 18.4%, and moisture is 20%.
Embodiment 4
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 1: 4 mixed of volume ratio, are obtained the mixed straw black liquor; Straw pulp black liquor by ammonium sulfite method fiber content 50mg/L wherein, Baume degrees 5, solid content=8%, pH9; Described alkaline straw-pulp black liquid fiber content 50mg/L, Baume degrees 5, solid content=8%, pH=10; Mixed straw pulp black liquor fiber content 50mg/L, Baume degrees 5, solid content=8%, pH=9.5;
(2) evaporation and concentration
The mixed straw black liquor is carried out 2 step flash distillations, obtain the mixed straw black liquor after the flash distillation.
Mixed straw black liquor after the flash distillation is carried out five imitate evaporation, five effect evaporation processes are countercurrent multi-effect evaporation, mixed straw black liquor after the flash distillation is imitated from V and is flowed into, heating steam is imitated from I and is flowed into, after mixed straw black liquor after the flash distillation is imitated heating evaporation through V effect, IV effect, III successively, become low half concentrated black liquid, after low half concentrated black liquid is imitated heating evaporation through II effect, I successively, become half concentrated black liquid, half concentrated black liquid is imitated through II successively again and I is imitated heating evaporation, become concentrated black liquid, be alkaline process and Ammonium Sulfite Method and mix concentrated straw pulp black liquor.
Above-mentioned heating steam temperature is 140 ℃, and pressure is 0.2MPa, becomes the cleaning condensed water through heat exchange after I is imitated inflow, and temperature is 105 ℃, and described cleaning condensed water carries out flash distillation again, and the steam that flashes off utilizes once more, to improve the heat energy utilization rate.
Five above-mentioned effect evaporations are respectively imitated pressure and are: I is imitated 20kPa, II effect-19kPa, III effect-58kPa, IV effect-73kPa, V effect-84kPa;
Each imitates black liquor temperature:
100 ℃ of I effects, 90 ℃ of II effects, 80 ℃ of III effects, 70 ℃ of IV effects, V are imitated 57 ℃
: each is imitated black liquid wave hairdressing and is respectively:
V effect 5, IV effect 9, III imitate 11; During for the first time through II effect and I effect, II effect 14, I imitate 18; During for the second time through II effect and I effect, II effect 23, I imitate 27.
Above-mentioned low half concentrated black liquid solid content is 18%, and Baume degrees is 11; Described half concentrated black liquid solid content is 29%, and Baume degrees is 18; Obtaining concentrated its solid content of straw pulp black liquor of alkaline process and Ammonium Sulfite Method mixing is 40%, and Baume degrees is 25, pH=8.
(3) spray drying
Alkaline process and the concentrated straw pulp black liquor of Ammonium Sulfite Method mixing are spray dried to dry powder, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, inlet temperature is 360 ℃ during spray drying, 85 ℃ of outlet temperatures.Alkali lignin content is 70% in gained alkaline process and the straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, ammonium lignin sulfonate content is 14.2%, and fulvic acid content is 5%, moisture 10%.
Embodiment 5
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 4: 1 mixed of volume ratio, are obtained the mixed straw black liquor;
Straw pulp black liquor by ammonium sulfite method fiber content 52mg/L wherein, Baume degrees 9, solid content=11%, pH9; Described alkaline straw-pulp black liquid fiber content 45mg/L, Baume degrees 9, solid content=11%, pH=13; Mixed straw pulp black liquor fiber content 48mg/L, Baume degrees 9, solid content=11%, pH=11;
(2) evaporation and concentration
The mixed straw black liquor is carried out five imitate evaporation, five effect evaporation processes are countercurrent multi-effect evaporation, mixed straw black liquor after the flash distillation is imitated from V and is flowed into, heating steam is imitated from I and is flowed into, after mixed straw black liquor after the flash distillation is imitated heating evaporation through V effect, IV effect, III successively, become low half concentrated black liquid, after low half concentrated black liquid is imitated heating evaporation through II effect, I successively, become half concentrated black liquid, half concentrated black liquid is imitated through II successively again and I is imitated heating evaporation, become concentrated black liquid, be alkaline process and Ammonium Sulfite Method and mix concentrated straw pulp black liquor.
Above-mentioned heating steam temperature is 140 ℃, and pressure is 0.4MPa, becomes the cleaning condensed water through heat exchange after I is imitated inflow, and temperature is 120 ℃, and described cleaning condensed water carries out flash distillation again, and the steam that flashes off utilizes once more, to improve the heat energy utilization rate.
Five above-mentioned effect evaporations are respectively imitated pressure and are: I is imitated 38kPa, and II is imitated 0kPa, III effect-40kPa, IV effect-60kPa, V effect-79kPa;
Each imitates black liquor temperature:
120 ℃ of I effects, 100 ℃ of II effects, 90 ℃ of III effects, 80 ℃ of IV effects, V are imitated 65 ℃
Each is imitated black liquid wave hairdressing and is respectively:
V effect 9, IV effect 12, III imitate 14; During for the first time through II effect and I effect, II effect 17, I imitate 21; During for the second time through II effect and I effect, II effect 25, I imitate 29.
Above-mentioned low half concentrated black liquid solid content is 20%, and Baume degrees is 14; Described half concentrated black liquid solid content is 35%, and Baume degrees is 21; Obtaining concentrated its solid content of straw pulp black liquor of alkaline process and Ammonium Sulfite Method mixing is 47%, and Baume degrees is 29, pH=6.
(3) spray drying
Alkaline process and the concentrated straw pulp black liquor of Ammonium Sulfite Method mixing are spray dried to dry powder, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, inlet temperature is 400 ℃ during spray drying, 130 ℃ of outlet temperatures; Alkali lignin content is 20% in gained alkaline process and the straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, ammonium lignin sulfonate content is 40%, and fulvic acid content is 30%, and moisture is 2%.
Embodiment 6
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 2: 1 mixed of volume ratio, are obtained the mixed straw black liquor; Straw pulp black liquor by ammonium sulfite method fiber content 100mg/L wherein, Baume degrees 9, solid content=10%, pH8; Described alkaline straw-pulp black liquid fiber content 50mg/L, Baume degrees 9, solid content=9%, pH=11; Mixed straw pulp black liquor fiber content 50mg/L, Baume degrees 9, solid content=9.7%, pH=9.6;
(2) evaporation and concentration
The mixed straw black liquor is carried out flash distillation, obtain the mixed straw black liquor after the flash distillation.
Mixed straw black liquor after the flash distillation is carried out five imitate evaporation, five effect evaporation processes are countercurrent multi-effect evaporation, mixed straw black liquor after the flash distillation is imitated from V and is flowed into, heating steam is imitated from I and is flowed into, after mixed straw black liquor after the flash distillation is imitated heating evaporation through V effect, IV effect, III successively, become low half concentrated black liquid, after low half concentrated black liquid is imitated heating evaporation through II effect, I successively, become half concentrated black liquid, half concentrated black liquid is imitated through II successively again and I is imitated heating evaporation, become concentrated black liquid, be alkaline process and Ammonium Sulfite Method and mix concentrated straw pulp black liquor.
Above-mentioned heating steam temperature is 140 ℃, and pressure is 0.3MPa, becomes the cleaning condensed water through heat exchange after I is imitated inflow, and temperature is 110 ℃, and described cleaning condensed water carries out flash distillation again, and the steam that flashes off utilizes once more, to improve the heat energy utilization rate.
Five above-mentioned effect evaporations are respectively imitated pressure and are: I is imitated 25kPa, II effect-10kPa, III effect-50kPa, IV effect-70kPa, V effect-80kPa;
Each imitates black liquor temperature:
110 ℃ of I effects, 95 ℃ of II effects, 85 ℃ of III effects, 75 ℃ of IV effects, V are imitated 60 ℃
Each is imitated black liquid wave hairdressing and is respectively:
I effect 25, II effect 18, III effect 15, IV effect 12, V imitate 9.
Above-mentioned low half concentrated black liquid solid content is 22%, and Baume degrees is 15; Described half concentrated black liquid solid content is 32%, and Baume degrees is 18; It is 42% that alkaline process that obtains and Ammonium Sulfite Method are mixed concentrated its solid content of straw pulp black liquor, and Baume degrees is 27, pH=7.
(3) slurry-spraying pelletizing
Alkaline process and Ammonium Sulfite Method are mixed concentrated straw pulp black liquor slurry-spraying pelletizing, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, slurry-spraying pelletizing machine head temperature is 550 ℃ during slurry-spraying pelletizing, 47 ℃ of tail temperature, returning charge amount 50%.Alkali lignin content is 36% in gained alkaline process and the straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, ammonium lignin sulfonate content is 35%, and fulvic acid content is 18%.
Embodiment 7
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid according to 3: 1 mixed of volume ratio, are obtained the mixed straw black liquor; Straw pulp black liquor by ammonium sulfite method fiber content 60mg/L wherein, Baume degrees 11, solid content=10%, pH8; Described alkaline straw-pulp black liquid fiber content 35mg/L, Baume degrees 11, solid content=11%, pH=10; Mixed straw pulp black liquor fiber content 40mg/L, Baume degrees 11, solid content=10.3%, pH=9;
(2) evaporation and concentration
The mixed straw black liquor is carried out 2 step flash distillations, obtain the mixed straw black liquor after the flash distillation.
Mixed straw black liquor after the flash distillation is carried out five imitate evaporation, five effect evaporation processes are countercurrent multi-effect evaporation, mixed straw black liquor after the flash distillation is imitated from V and is flowed into, heating steam is imitated from I and is flowed into, after mixed straw black liquor after the flash distillation is imitated heating evaporation through V effect, IV effect, III successively, become low half concentrated black liquid, after low half concentrated black liquid is imitated heating evaporation through II effect, I successively, become half concentrated black liquid, half concentrated black liquid is imitated through II successively again and I is imitated heating evaporation, become concentrated black liquid, be alkaline process and Ammonium Sulfite Method and mix concentrated straw pulp black liquor.
Above-mentioned heating steam temperature is 140 ℃, and pressure is 0.3MPa, becomes the cleaning condensed water through heat exchange after I is imitated inflow, and temperature is 112 ℃, and described cleaning condensed water carries out flash distillation again, and the steam that flashes off utilizes once more, to improve the heat energy utilization rate.
Five above-mentioned effect evaporations are respectively imitated pressure and are: I is imitated 28kPa, II effect-12kPa, III effect-45kPa, IV effect-65kPa, V effect-82kPa;
Each imitates black liquor temperature:
115 ℃ of I effects, 98 ℃ of II effects, 86 ℃ of III effects, 73 ℃ of IV effects, V are imitated 58 ℃
Each is imitated black liquid wave hairdressing and is respectively:
I effect 24, II effect 16, III effect 15, IV effect 12, V imitate 8.
Above-mentioned low half concentrated black liquid solid content is 21%, and Baume degrees is 16; Described half concentrated black liquid solid content is 33%, and Baume degrees is 19; It is 42% that alkaline process that obtains and Ammonium Sulfite Method are mixed concentrated its solid content of straw pulp black liquor, and Baume degrees is 28, pH=6.8.
(3) slurry-spraying pelletizing
Alkaline process and Ammonium Sulfite Method are mixed concentrated straw pulp black liquor slurry-spraying pelletizing, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, slurry-spraying pelletizing machine head temperature is 600 ℃ during slurry-spraying pelletizing, 55 ℃ of tail temperature, returning charge amount 60%.Alkali lignin content is 30% in gained alkaline process and the straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, ammonium lignin sulfonate content is 38%, and fulvic acid content is 22%, moisture 5%.
Embodiment 8
Other condition is with embodiment 7, and straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are 10: 1 according to volume ratio, obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, alkali lignin content is 15%, ammonium lignin sulfonate content is 45%, and fulvic acid content is 25%, moisture 10%.
Embodiment 9
Other condition is with embodiment 4, and straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are 1: 10 according to volume ratio, obtain alkaline process and straw pulp black liquor by ammonium sulfite method mixing concentrated dry thing, alkali lignin content is 80%, ammonium lignin sulfonate content is 5%, and fulvic acid content is 3%, moisture 6%.
Claims (15)
1. the preparation method of alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter is characterized in that, comprises
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are mixed, obtain the mixed straw black liquor;
(2) evaporation and concentration
The mixed straw black liquor is carried out evaporation and concentration till moisture weight percentage≤20%, obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
2. the preparation method of alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter is characterized in that, comprising:
(1) mixes
Straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid are mixed, obtain the mixed straw black liquor;
(2) evaporation and concentration
It is 40-47% that the mixed straw black liquor is carried out evaporation and concentration to solid content, and Baume degrees is 25-29, obtains alkaline process and Ammonium Sulfite Method and mixes concentrated straw pulp black liquor;
(3) drying
Alkaline process and the concentrated straw pulp black liquor of Ammonium Sulfite Method mixing are dried to solid content, promptly obtain alkaline process and straw pulp black liquor by ammonium sulfite method hybrid dry matter.
3. preparation method according to claim 2 is characterized in that, the drying in the described step (3) is slurry-spraying pelletizing or spray drying.
4. preparation method according to claim 2 is characterized in that, also comprises before described step (2) evaporation and concentration mixed straw black liquor is carried out flash distillation.
5. preparation method according to claim 4 is characterized in that, described flash distillation is carried out 2 times continuously.
6. preparation method according to claim 2 is characterized in that, described evaporation and concentration is a multiple-effect evaporation.
7. preparation method according to claim 6 is characterized in that, described multiple-effect evaporation is five effect evaporations.
8. preparation method according to claim 7, it is characterized in that, described five effect evaporation processes are countercurrent multi-effect evaporation, mixed straw black liquor after the flash distillation is imitated from V and is flowed into, heating steam is imitated from I and is flowed into, after mixed straw black liquor after the flash distillation is imitated heating evaporation through V effect, IV effect, III successively, become low half concentrated black liquid, after low half concentrated black liquid is imitated heating evaporation through II effect, I successively, become half concentrated black liquid, half concentrated black liquid is imitated through II successively again and I is imitated heating evaporation, becomes concentrated black liquid, is alkaline process and Ammonium Sulfite Method and mixes concentrated straw pulp black liquor.
9. preparation method according to claim 8 is characterized in that, described five effect evaporations are respectively imitated pressure and are: I is imitated 20-38kPa, II effect-19～0kPa, III effect-58～-40kPa, IV effect-73～-60kPa, V effect-84～-79kPa;
Each imitates black liquor temperature:
100-120 ℃ of I effect, 90-100 ℃ of II effect, 80-90 ℃ of III effect, 70-80 ℃ of IV effect, V effect are respectively imitated black liquid wave hairdressing for 57-65 ℃ and are respectively:
V is imitated 5-9, IV and is imitated 9-12, III effect 11-14; During for the first time through II effect and I effect, II is imitated 14-17, I and is imitated 18-21; During for the second time through II effect and I effect, II is imitated 23-25, I and is imitated 27-29;
Described low half concentrated black liquid solid content is 20-25%, and Baume degrees is 11-14; Described half concentrated black liquid solid content is 30-35%, and Baume degrees is 18-21;
Described heating steam temperature is 140 ℃, and pressure is 0.2-0.4MPa, becomes the cleaning condensed water through heat exchange after I is imitated inflow, temperature is 105 ℃-120 ℃, described cleaning condensed water carries out flash distillation again, and the steam that flashes off utilizes once more, to improve the heat energy utilization rate.
10. preparation method according to claim 3 is characterized in that, inlet temperature is 360-400 ℃ during described spray drying, outlet temperature 85-130 ℃; Slurry-spraying pelletizing machine head temperature is 550～600 ℃ during described slurry-spraying pelletizing, 47-55 ℃ of tail temperature, returning charge amount 〉=50%.
11. preparation method according to claim 1 and 2 is characterized in that, the volume ratio of straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1 in the described step (1): 100-100: 1; Described straw pulp black liquor by ammonium sulfite method content of cellulose≤200mg/L, Baume degrees 2-9, solid content are 4-15%, pH is 7-10; Described alkaline straw-pulp black liquid content of cellulose≤200mg/L, Baume degrees 2-9, solid content are 4-15%, pH is 9-13.
12. preparation method according to claim 11 is characterized in that, the volume ratio of straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1 in the described step (1): 10-10: 1.
13. preparation method according to claim 12 is characterized in that, the volume ratio of straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1 in the described step (1): 4-4: 1.
14. preparation method according to claim 1 and 2, it is characterized in that, alkali lignin content is that 0.1-90%, ammonium lignin sulfonate content are 0.1-60% in described alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, and fulvic acid content is 1-35%, and moisture is 0-20%.
15. preparation method according to claim 14, it is characterized in that, alkali lignin content is that 20-70%, ammonium lignin sulfonate content are 15-40% in described alkaline process and the straw pulp black liquor by ammonium sulfite method hybrid dry matter, and fulvic acid content is 5-30%, and moisture is 0-10%.
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| CN103318980B (en) * | 2013-07-03 | 2014-08-20 | 金东纸业（江苏）股份有限公司 | Processing device and processing method of pulping waste water |
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| CN1141983A (en) * | 1995-07-28 | 1997-02-05 | 李保民 | Method for comprehensive control and treatment of black liquor from alkali paper-making |
| CN1153843A (en) * | 1996-09-10 | 1997-07-09 | 刘友会 | Alkali process for treating black liquor |
| CN1298985A (en) * | 2001-01-12 | 2001-06-13 | 潍坊学院 | Alkali recovery process for black paper-making liquid of grass pulp |
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