CN102363928A - Clean pulp preparation process using reaction of KOH and H2O2 - Google Patents
Clean pulp preparation process using reaction of KOH and H2O2 Download PDFInfo
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- CN102363928A CN102363928A CN2011102967260A CN201110296726A CN102363928A CN 102363928 A CN102363928 A CN 102363928A CN 2011102967260 A CN2011102967260 A CN 2011102967260A CN 201110296726 A CN201110296726 A CN 201110296726A CN 102363928 A CN102363928 A CN 102363928A
- Authority
- CN
- China
- Prior art keywords
- raw material
- pulp
- koh
- consumption
- mashing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000009835 boiling Methods 0.000 claims abstract description 13
- 239000010902 straw Substances 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims description 17
- 238000005360 mashing Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- 235000013322 soy milk Nutrition 0.000 claims description 6
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000010411 cooking Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 235000011837 pasties Nutrition 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 235000014676 Phragmites communis Nutrition 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
Landscapes
- Paper (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a clean pulp preparation process using reaction of KOH and H2O2, and belongs to the field of papermaking. The process is characterized by comprising the following steps of: cooking water, straw raw material, KOH and primary cooking aid till boiling in a closed pulp cooking pot, and stirring; adding H2O2 and secondary cooking aid within 1 hour, and cooking for 1 to 3 hours till the raw material is pasty; and filtering, washing pulp, and obtaining waste liquor and crude pulp. The process is improved from the source of generating black liquor, so that the black liquor is obviously reduced, the chemical oxygen demand (COD) value of the waste liquor is reduced, the pulp yield is improved, and the strength and the whiteness of the obtained crude pulp accord with the production requirements. The process has the characteristics of simplicity, low energy consumption, raw material economization and the like.
Description
Technical field
The present invention relates to a kind of pulping and paper-making new technology and environmental protection new method, relate in particular to the papermaking straw pulp new cleanproduction process.
Background technology
Paper industry is a pillar industry of China, and from 2000 to 2009, the annual production of Chinese paper-making industry was promoted to 8,640 ten thousand tons from 3,050 ten thousand tons, increases nearly twice in 10 years, and annual average rate of increase reaches more than 10%.At present, the waste water that paper industry accounts for total emission volumn 50% does not carry out processing up to standard as yet, and the paper-making industrial waste water pollution problem is still very serious.The unit product wastewater discharge of China's pulp and paper industry that with non-wood pulp is the master is higher, and the various waste water that mainly produce from pulping process are wherein serious with the pollution of black digestion liquid, account for about 90% of pulping and paper-making gross contamination deposits yields amount.Lignin and derivative thereof that it contains difficult degradation are a kind of overbasic organic wastewater, and characteristics are that alkalescence is strong, colourity is high, content of organics is high, and difficult treatment is prone to cause the heavy damage of water pollution and ecological environment.
In recent years, the improvement of black liquor has also obtained certain progress, but is mostly the end treatment technology, like Silvola recovery, chemical flocculation, acid-precipitation method, membrane separation process, bioanalysis.The shortcoming of end treatment is more; Many like structure unit, the operation power cost is high, add that pharmaceutical quantities is big, easy generation of secondary pollution etc.; It is thus clear that can not eliminate the pollution of black liquor of pulp making effectively through traditional end improvement, not in full conformity with the environmental protection concept of cleaner production and sustainable development for environment.
Patented invention about cleaning pulping also has a lot:
CN101200862A discloses a kind of grass class or the broad-leaved class is the clean pulping process of raw material; Utilize urea and neutral sodium sulfite to come delignification through high dense mill of twice and high density bleaching insulation storehouse; Belong to sulfite pulping, and in this process, add hydrogen peroxide, NaOH and oxalic acid etc. bleaches.But this technology is still kept away the problem of the red liquid of unavoidable generation, and reuse and intractability are big, and the possibility of really implementing waste water (liquid) zero-emission is little.
CN101929089A discloses a kind of equipment of using the clean pulping process of catalytic wet oxidation prepared in reaction paper pulp and implementing this technology, is characterized in the catalytic wet oxidation agitated reactor, utilizing the oxygen that causes through catalyst in water body, to produce the hydroxyl radical free radical isoreactivity group that has strong oxidized form in a large number and removes lignin and decompose chromophore.This technological requirement reaction temperature high (150-300 ℃), pressure big (1-15Mpa), reaction time long (1-24h), the catalyst cost is high, and its equipment investment and production cost all are higher than traditional paper technology.
CN101613969A discloses a kind of pulping process of paper product pulp; Pretreated raw material reacted with strong alkaline substance and strong oxidizer under HTHP remove lignin; This technological requirement is reflected under the high pressure (1-6atm) carries out; The oxidant consumption has reached 1.2 times of raw material, and consumption is many, and production cost is higher.Though and the waste liquid that produces is lower than other black liquid consistency, the subsequent treatment difficulty is still bigger.
CN1847520 discloses a kind of hydrogen peroxide that utilizes and has met the violent paper pulp method of producing of decomposing of excesses of basic material; Alkaline matter is a NaOH described in these technology claims; When being raw material with straw, reed etc.; NaOH as the effect of alkaline matter not as potassium hydroxide, and in this patent undeclared gained pulp quality and waste liquid character related data index, how be difficult to judge its implementation result.
Summary of the invention
The present invention provides a kind of KOH of utilization and H
2O
2The clean pulping process that reacts, this reaction is violent and discharge heat energy, make this improvement technology can under normal pressure, carry out pulping by cooking, and pulping waste liquor is bleached in digestion process simultaneously.Its objective is according to the cleaner production theory pulping process of enterprises in pulp and paper industry is carried out technological innovation; Improve technology from the source that black liquor produces, simplify reaction condition to greatest extent, reduce black liquid and produce; Promote thick slurry quality, to realize the doulbe-sides' victory target of environmental protection and paper.
Technical scheme of the present invention is following:
(1) grass as raw material is dry, dedusting, can prescind to length less than 2cm;
(2) in airtight soymilk cooker, add entry, be heated to boiling, put into raw material, KOH and digesting assistant mashing off boiling extremely once more for the first time after prescinding, stir; After being no more than 1h, add H2O2 and the digesting assistant second time, mashing off 1h-3h becomes scattered paste shape until raw material, stops mashing off; The KOH consumption is 5%-11%; The H2O2 consumption is 10%-18%; Digesting assistant is Na2SO3, Na2SiO3 and DTPMP for the first time, and consumption is: Na2SO31%, Na2SiO310%, DTPMP1%; Digesting assistant is (NH for the second time
2)
2CSO
2, consumption is 0.3%; The mashing off water consumption is 3t water/1t straw, and reaction temperature is 80-100 ℃, and reaction pressure is a normal pressure;
(3) filter pulp washing, obtain waste liquid and thick slurry;
Beneficial effect of the present invention is compared with traditional soda processes, obviously reduces the generation of black liquor, reduces waste liquid COD value, has improved pulping yield, and thick slurry intensity that obtains and the equal accords with production requirement of whiteness.In the pulping process, adopt atmospheric cooking, temperature 80-100 ℃, than traditional soda processes HTHP pulping process, energy consumption reduces.
The specific embodiment
Specify the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1:
With the 1t straw after the dry dedusting prescind to length less than 2cm, process straw raw material.In airtight soymilk cooker, add 3t water, be heated to boiling, put into 1t straw raw material, 50kgKOH, 10kgNa
2SO
3, 100kgNa
2SiO
3, 10kgDTPMP, 170kgH
2O
2And 3kg (NH
2)
2CSO
2, mashing off is to boiling once more, and every separated 3-4min stirs once, and straw becomes scattered paste shape behind the 1h, stops mashing off.Filter pulp washing, gained waste liquid COD value is 5840mg/L, and thick slurry yield is 63.18%, and thick pulp brightness is 40.97%, and permanganate number is 19.6.
Embodiment 2:
With the 1t stalk after the dry dedusting prescind to length less than 2cm, process stalk.In airtight soymilk cooker, add 3t water, be heated to boiling, put into 1t stalk, 100kgKOH, 10kgNa2SO3,100kgNa2SiO3,10kgDTPMP mashing off to boiling once more, every separated 3-4min stirs once.Behind the 1h, add 100kgH
2O
2And 3kg (NH
2)
2CSO
2, stalk becomes scattered paste shape behind the 2h, stops mashing off.Filter pulp washing, gained waste liquid COD value is 5910mg/L, and thick slurry yield is 62.56%, and thick pulp brightness is 31.25%, and permanganate number is 17.4.
Embodiment 3:
With the 1t wheat straw after the dry dedusting prescind to length less than 2cm, process wheat straw raw material.In airtight soymilk cooker, add 3t water, be heated to boiling, put into 1t wheat straw raw material, 100kgKOH, 10kgNa
2SO
3, 100kgNa
2SiO
3, the 10kgDTPMP mashing off is to boiling once more, every stir once at a distance from 3-4min.0.5h after, add 180kgH
2O
2And 3kg (NH
2)
2CSO
2, wheat straw becomes scattered paste shape behind the 2h, stops mashing off.Filter pulp washing, gained waste liquid COD value is 6240mg/L, and thick slurry yield is 58.61%, and thick pulp brightness is 39.28%, and permanganate number is 13.4.
Embodiment 4:
With the 1t reed after the dry dedusting prescind to length less than 2cm, process the reed raw material.In airtight soymilk cooker, add 3t water, be heated to boiling, put into 1t reed raw material, 110kgKOH, 10kgNa
2SO
3, 100kgNa
2SiO
3, the 10kgDTPMP mashing off is to boiling once more, every stir once at a distance from 3-4min.0.5h after, add 170kgH
2O
2And 3kg (NH
2)
2CSO
2, reed becomes scattered paste shape behind the 3h, stops mashing off.Filter pulp washing, gained waste liquid COD value is 6430mg/L, and thick slurry yield is 52.26%, and thick pulp brightness is 38.02%, and permanganate number is 12.5.
Claims (2)
1. one kind is utilized KOH and H
2O
2The clean pulping process that reacts is characterized in that may further comprise the steps:
(1) with grass as raw material drying, dedusting, prescind;
(2) in airtight soymilk cooker, add entry, be heated to boiling, put into raw material, KOH and digesting assistant mashing off boiling extremely once more for the first time after prescinding, stir; After being no more than 1h, add H
2O
2With the digesting assistant second time, mashing off 1h-3h becomes scattered paste shape until raw material, stops mashing off; The KOH consumption is 5%-11%; H
2O
2Consumption is 10%-18%; Digesting assistant is Na for the first time
2SO
3, Na
2SiO
3And DTPMP, consumption is: Na
2SO
31%, Na
2SiO
310%, DTPMP1%; Digesting assistant is (NH for the second time
2)
2CSO
2, consumption is 0.3%; The mashing off water consumption is 3t water/1t straw, and reaction temperature is 80-100 ℃, and reaction pressure is a normal pressure;
(3) filter pulp washing, obtain waste liquid and thick slurry.
2. technology as claimed in claim 1 is characterized in that, the raw material of use prescinds back length less than 2cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110296726 CN102363928B (en) | 2011-09-27 | 2011-09-27 | Clean pulp preparation process using reaction of KOH and H2O2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110296726 CN102363928B (en) | 2011-09-27 | 2011-09-27 | Clean pulp preparation process using reaction of KOH and H2O2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102363928A true CN102363928A (en) | 2012-02-29 |
| CN102363928B CN102363928B (en) | 2013-04-17 |
Family
ID=45690521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110296726 Expired - Fee Related CN102363928B (en) | 2011-09-27 | 2011-09-27 | Clean pulp preparation process using reaction of KOH and H2O2 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102363928B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083882A (en) * | 1992-09-10 | 1994-03-16 | 乔治·J·泰森 | The delignification of non-wooden property biogenic accumulation thing |
| US5306392A (en) * | 1990-09-14 | 1994-04-26 | Akio Mita | Process for preparing pulp using potassium-based alkaline solution |
| CN101532260A (en) * | 2009-04-17 | 2009-09-16 | 华南理工大学 | Method for pulping by cooking solid base in plant fiber |
| CN101823002A (en) * | 2010-04-20 | 2010-09-08 | 金永安 | Alkali-hydrogen peroxide method-based cooking catalyst and clean pulping process |
| CN101929089A (en) * | 2009-06-22 | 2010-12-29 | 北京西桥阳光科技有限公司 | Wet catalytic oxidation clean pulping process and equipment for implementing same |
-
2011
- 2011-09-27 CN CN 201110296726 patent/CN102363928B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306392A (en) * | 1990-09-14 | 1994-04-26 | Akio Mita | Process for preparing pulp using potassium-based alkaline solution |
| CN1083882A (en) * | 1992-09-10 | 1994-03-16 | 乔治·J·泰森 | The delignification of non-wooden property biogenic accumulation thing |
| CN101532260A (en) * | 2009-04-17 | 2009-09-16 | 华南理工大学 | Method for pulping by cooking solid base in plant fiber |
| CN101929089A (en) * | 2009-06-22 | 2010-12-29 | 北京西桥阳光科技有限公司 | Wet catalytic oxidation clean pulping process and equipment for implementing same |
| CN101823002A (en) * | 2010-04-20 | 2010-09-08 | 金永安 | Alkali-hydrogen peroxide method-based cooking catalyst and clean pulping process |
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| Publication number | Publication date |
|---|---|
| CN102363928B (en) | 2013-04-17 |
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Granted publication date: 20130417 |