NO157828B - TREATMENT OF TREFLIS. - Google Patents
TREATMENT OF TREFLIS. Download PDFInfo
- Publication number
- NO157828B NO157828B NO834751A NO834751A NO157828B NO 157828 B NO157828 B NO 157828B NO 834751 A NO834751 A NO 834751A NO 834751 A NO834751 A NO 834751A NO 157828 B NO157828 B NO 157828B
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- Norway
- Prior art keywords
- potassium
- sodium
- alkali metal
- mixed
- hour
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims description 50
- 229910052700 potassium Chemical class 0.000 claims description 40
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 37
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 37
- 239000011591 potassium Chemical class 0.000 claims description 37
- 229910052708 sodium Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 229920000388 Polyphosphate Polymers 0.000 claims description 16
- 239000001205 polyphosphate Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 235000011176 polyphosphates Nutrition 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 2
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 abstract 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 abstract 1
- 229920001131 Pulp (paper) Polymers 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000002023 wood Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052585 phosphate mineral Inorganic materials 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 150000003112 potassium compounds Chemical class 0.000 description 4
- 239000001120 potassium sulphate Substances 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 2
- 244000075850 Avena orientalis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 235000019828 potassium polyphosphate Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 239000012066 reaction slurry Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Classifications
-
- 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
- D21C1/00—Pretreatment of the finely-divided materials before digesting
Landscapes
- Paper (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
Oppfinnelsen vedrrer behandling av treflis for fremstilling av kjemi-termomekanisk masse, såkalt CTMP. Etter predamping og impregnering, vasking og tørking, men før sluttimpregnering, forvarming og raffinering holdes flisen under et mellomliggende trinn ved en temperatur på minst 50° under en tid på minst 10 minutt.The invention relates to the treatment of wood chips for the production of chemical thermomechanical pulp, so-called CTMP. After pre-evaporation and impregnation, washing and drying, but before final impregnation, preheating and refining, the tile is kept during an intermediate step at a temperature of at least 50 ° for a period of at least 10 minutes.
Description
Fremgangsmåte til fremstilling av blandede polyfosfatsalter av natrium og kalium. Process for the production of mixed polyphosphate salts of sodium and potassium.
Foreliggende oppfinnelse vedrorer en fremgangsmåte til fremstilling av blandede polyfosfatsalter av natrium og kalium. The present invention relates to a method for producing mixed polyphosphate salts of sodium and potassium.
Man kjenner til at alkalimetallsaltene av polyfosforsyre-anioner, og særlig natriumpyrofosfatet Na^PgOy og natriumtripoly-fosfatet Na^P^<O->^Q, har en utbredt industriell anvendelse, særlig til fremstilling av utlutningsopplosninger, kompleksdannere og gjodnings-midler. It is known that the alkali metal salts of polyphosphoric acid anions, and in particular the sodium pyrophosphate Na^PgOy and the sodium tripolyphosphate Na^P^<O->^Q, have widespread industrial use, particularly for the production of leaching solutions, complexing agents and fertilisers.
Selv om nevnte ■natriumsalter har fått en utbredt anvendelse, Although the aforementioned ■sodium salts have gained widespread use,
har man foreslått i stedet å bruke blandede salter av kalium og natrium-polyfosforsyrer, som vanligvis har en hoyere opploselighet i vann enn de tilsvarende natriumforbindelser. Bruken av disse kalium- og natriumsalter har imidlertid hittil vært begrenset, fordi de kjente metoder it has been suggested instead to use mixed salts of potassium and sodium polyphosphoric acids, which usually have a higher solubility in water than the corresponding sodium compounds. However, the use of these potassium and sodium salts has so far been limited, because the known methods
til fremstilling av disse forbindelser er mindre gode. for the production of these compounds are less good.
Ifolge en av de allerede kjente metoder fremstilles visse blandede kalium- og natriumpolyfosfater ut fra en vandig opplosning av tilsvarende polyfosforsyre, og natrium- og kaliumforbindelser i form av oksyder eller karbonater. Denne metode frembyr den ulempe at det hertil må anvendes spesielt tunge og vanskelig bearbeidbare kalium-forbindelser. According to one of the already known methods, certain mixed potassium and sodium polyphosphates are produced from an aqueous solution of corresponding polyphosphoric acid, and sodium and potassium compounds in the form of oxides or carbonates. This method presents the disadvantage that particularly heavy and difficult-to-process potassium compounds must be used for this.
I henhold til en annen, likeledes kjent, metode fremstilles visse blandede salter av kalium- og natriumpolyfosfater ved hjelp av kaliumklorid. En stor ulempe ved denne metode består i at klorionet helt må fjernes fra reaksjonsblandingen, og i at denne reaksjonsblan-ding er meget korrosiv. According to another, likewise known, method, certain mixed salts of potassium and sodium polyphosphates are prepared using potassium chloride. A major disadvantage of this method is that the chlorine ion must be completely removed from the reaction mixture, and that this reaction mixture is very corrosive.
Sokeren har nå funnet en spesielt fordelaktig fremgangsmåte til fremstilling av blandede polyfosfatsalter av natrium og kalium, hvortil det ikke anvendes nevnte sterkt etsende forbindelser. Sokeren has now found a particularly advantageous method for the production of mixed polyphosphate salts of sodium and potassium, for which the aforementioned highly corrosive compounds are not used.
Foreliggende oppfinnelse angår således en fremgangsmåte til fremstilling av blandede polyfosfatsalter av natrium og kalium med generell formel (Na,K)x+2 px°3x+j_ > hvor x er minst lik 2, hvorved naturlig kalsiumfosfat omsettes med en opplosning av fosforsyre og et alkalimetallsulfat som kalium- og/eller natriumsulfat, hvor mengden tilsatt alkalimetallsalt beregnes ut fra mengde opploselige Ca-ioner i naturfosfatet som kan reagere til kalsiumsulfat, hvoretter faste stoffer i den således fremkomne grot fraskilles og det resulterende filtrat delvis nøytraliseres med minst ett alkalimetallsalt i form av oksyder, hydroksyder, karbonater eller bikarbonater av natrium og/eller kalium, hvorved denne partielle nøytralisering utfores slik at forholdet mellom det totale antall alkalimetallioner og antall fosforatomer i reaksjonsblandingen i det vesentlige er lik x + 2 , hvor x The present invention thus relates to a method for producing mixed polyphosphate salts of sodium and potassium with the general formula (Na,K)x+2 px°3x+j_ > where x is at least equal to 2, whereby natural calcium phosphate is reacted with a solution of phosphoric acid and a alkali metal sulfate such as potassium and/or sodium sulfate, where the amount of added alkali metal salt is calculated from the amount of soluble Ca ions in the natural phosphate that can react to form calcium sulfate, after which solids in the resulting slurry are separated and the resulting filtrate is partially neutralized with at least one alkali metal salt in the form of oxides, hydroxides, carbonates or bicarbonates of sodium and/or potassium, whereby this partial neutralization is carried out so that the ratio between the total number of alkali metal ions and the number of phosphorus atoms in the reaction mixture is essentially equal to x + 2, where x
2 2
er som definert ovenfor, hvoretter den delvis nøytraliserte opplosning filtreres og inndampes og brennes til blandede polyfosfatsalter av natrium og kalium. is as defined above, after which the partially neutralized solution is filtered and evaporated and burned to mixed polyphosphate salts of sodium and potassium.
Spesielt anvendes fremgangsmåten i henhold til oppfinnelsen til fremstilling av blandede pyrofosfater av natrium og kalium med generell formel (Na,K) ^PgO,-, , samt til fremstilling av blandede tripolyfosfater av natrium og kalium med generell formel (Na,K)^P^O-^. In particular, the method according to the invention is used for the production of mixed pyrophosphates of sodium and potassium with the general formula (Na,K) ^PgO,-, , as well as for the production of mixed tripolyphosphates of sodium and potassium with the general formula (Na,K)^P ^O-^.
Det ligger imidlertid innenfor oppfinnelsens ramme å frem-stille, ifolge oppfinnelsens fremgangsmåte, blandede polyfosfater av kalium og natrium som er kondensert i en hoyere grad enn nevnte blandede tripolyfosfat av kalium og natrium, spesielt blandede tetra- og penta-polyfosfater av natrium og kalium, og også forskjellige andre blan-dinger av natrium- og kaliumsalter av polyfosfater. However, it is within the scope of the invention to produce, according to the method of the invention, mixed polyphosphates of potassium and sodium which are condensed to a higher degree than said mixed tripolyphosphate of potassium and sodium, especially mixed tetra- and penta-polyphosphates of sodium and potassium, and also various other mixtures of sodium and potassium salts of polyphosphates.
I henhold til oppfinnelsen fremstilles fortrinnsvis blandede polyfosfater av natrium og kalium, hvori det molekylære forhold mellom kaliumioner og det totale antall alkalimetallioner ligger mellom 0,3 According to the invention, mixed polyphosphates of sodium and potassium are preferably produced, in which the molecular ratio between potassium ions and the total number of alkali metal ions lies between 0.3
og 0,7- and 0.7-
Det er videre fordelaktig i henhold til oppfinnelsen å omsette naturlig fosfat med en opplosning av fosforsyre og kaliumsulfat. It is further advantageous according to the invention to react natural phosphate with a solution of phosphoric acid and potassium sulphate.
De forskjellige reaksjoner og også den totale prosess, kan utfores kontinuerlig eller diskontinuerlig. Fortrinnsvis utfores oppfinnelsens fremgangsmåte imidlertid kontinuerlig gjennom alle fremstil-lingsfaser. The various reactions and also the overall process can be carried out continuously or discontinuously. Preferably, however, the method of the invention is carried out continuously throughout all production phases.
Nedenfor beskrives en helkontinuerlig foretrukken utforelses-måte av oppfinnelsens fremgangsmåte, bestående av fem hovedtrinn: forste trinn utfores i en beholder utstyrt med roreverk, hvori man kontinuerlig innforer: Below is described a fully continuous preferred method of carrying out the method of the invention, consisting of five main steps: the first step is carried out in a container equipped with agitator, into which you continuously introduce:
a) en opplosning av fosforsyre som fortrinnsvis inneholder mellom 25 a) a solution of phosphoric acid which preferably contains between 25
og 32 vektsprosent ^ 2^^' and 32 percent by weight ^ 2^^'
b) kaliumsulfat, fortrinnsvis knust til granulater med storrelse b) potassium sulphate, preferably crushed into size granules
under 1 mm, less than 1 mm,
c) fosfat-mineral bestående av kalsiumfosfat, fortrinnsvis knust. c) phosphate mineral consisting of calcium phosphate, preferably crushed.
I lopet av denne operasjon innfores en total mengde kaliumioner, såo ledes at denne mengde tilsvarer et molforhold K 2 O under verdien 0,5. <P>2°5 In the course of this operation, a total quantity of potassium ions is introduced, so it is assumed that this quantity corresponds to a molar ratio of K 2 O below the value 0.5. <P>2°5
Som det allerede er anfort, beregnes mengden alkalimetall som skal tilsettes ut fra den mengde opploselige kalsiumioner som finnes i naturfosfatet, idet disse kalsiumioner vil felles som sulfat. As has already been stated, the amount of alkali metal to be added is calculated from the amount of soluble calcium ions found in the natural phosphate, as these calcium ions will precipitate as sulphate.
Den midlere reaksjonstid for dette forste trinn ligger vanligvis mellom 2 og 6 timer, når det anvendes en reaksjonstemperatur på mellom 35 °S 55°G. Fortrinnsvis arbéider man nær 50°C og med en reaksjonstid i nærheten av 5 timer. Under fremstillingens andre trinn behandles groten fra foregående behandling i nevnte reaksjonsbeholder i den hensikt å fraskille faste utfelte stoffer. The average reaction time for this first step is usually between 2 and 6 hours, when a reaction temperature of between 35°S 55°G is used. Preferably, you work at close to 50°C and with a reaction time of close to 5 hours. During the second stage of the production, the groats from the previous treatment are processed in the aforementioned reaction vessel with the aim of separating solid precipitated substances.
Denne fraskilling skjer ved hjelp av et kontinuerlig vakuumfilter, som f.eks. et båndfilter eller et trommelfilter, og filter- This separation takes place with the help of a continuous vacuum filter, such as a belt filter or a drum filter, and filter-
kaken vaskes med vann hvoretter hovedfiltratet samt vaskevannene slås sammen. the cake is washed with water, after which the main filtrate and the washing waters are combined.
Under det tredje trinn fores i kontinuerlige trinn det klare filtrat inn i en beholder utstyrt med rorer hvori man også innforer, likeledes kontinuerlig, forbindelser av natrium eller kalium, i form av oksyder, hydroksyder, karbonater eller bikarbonater. Denne tilsetning av natrium- og kalium-forbindelser skjer inntil man oppnår et molekylarforhold Na + K som i det vesentlige er lik x + 2 , hvor x During the third step, the clear filtrate is fed in continuous steps into a container equipped with stirrups into which sodium or potassium compounds, in the form of oxides, hydroxides, carbonates or bicarbonates, are also continuously introduced. This addition of sodium and potassium compounds takes place until a molecular ratio Na + K is obtained which is essentially equal to x + 2 , where x
P ~ P~
har den verdi som onskes i produktet med formel (Na >K)x+2Px^3x+l' °^ idet man samtidig sorger for å holde et forhold K på mellom 0,3 og 0,7. Na + K has the desired value in the product with formula (Na >K)x+2Px^3x+l' °^ while at the same time taking care to keep a ratio K of between 0.3 and 0.7. Na + K
Til fremstilling av et blandet pyrofasfat av natrium og kalium med formel (Na,K)^P20^, får man i reaks jonsblandingen således et mole-kylarf orhold Na + K som er omtrent lik 2, og til fremstilling av et blandet tripolyfosfat av natrium og kalium med formel (Na,K)^P^0jQ får man et molekylarforhold Na + K som er lik 5/3'For the production of a mixed pyrophosphate of sodium and potassium with the formula (Na,K)^P20^, one thus obtains in the reaction mixture a molecular ratio of Na + K which is approximately equal to 2, and for the production of a mixed tripolyphosphate of sodium and potassium with the formula (Na,K)^P^0jQ gives a molecular ratio Na + K equal to 5/3'
I lopet av denne operasjon holdes temperaturen vanligvis mellom 50 og 100°C og operasjonens varighet ligger vanligvis mellom 30 minutter og 2 timer. Fortrinnsvis arbeider man i nærheten av <r>jO°C og i et tids-rom som ligger omkring 45 minutter. In the course of this operation, the temperature is usually kept between 50 and 100°C and the duration of the operation is usually between 30 minutes and 2 hours. Preferably, one works in the vicinity of <r>jO°C and in a time period of around 45 minutes.
Dette tredje trinn av fremgangsmåten kan fortrinnsvis utfSres kontinuerlig i to trinn, idet man forst innforer de alkaliske forbindelser, slik at man får et molforhold: alkalimetall som ligger mellom This third step of the method can preferably be carried out continuously in two steps, first introducing the alkaline compounds, so that a molar ratio: alkali metal that lies between
F F
1 og 1,20, hvoretter man regulerer molforholdet ved hjelp av fornyet tilsetning av alkaliske forbindelser , slik at forholdet alkalimetall blir lik x + 2 . P 1 and 1.20, after which the molar ratio is adjusted by means of renewed addition of alkaline compounds, so that the alkali metal ratio is equal to x + 2. P
x x
Det fjerde trinn består i en kontinuerlig filtrering av opplosningen fra tredje trinn, og filterkaken vaskes med vann som fores tilbake til filtratet fra forste filtrering. The fourth stage consists of a continuous filtration of the solution from the third stage, and the filter cake is washed with water that is fed back to the filtrate from the first filtration.
Femte trinn består i at væsken fra fjerde trinn inndampes og ved kalsinering fores så et sluttprodukt bestående av blandede polyfosfatsalter av natrium og kalium. The fifth step consists in the liquid from the fourth step being evaporated and, by calcination, a final product consisting of mixed polyphosphate salts of sodium and potassium is then prepared.
Fortrinnsvis utfores dette kalsineringstrinn med tilbakeføring av en del av det ferdige produkt til den forutgående behandling, således: Væsken fra tredje trinn inndampes forst i en flertrinnsinn-damper inntil man oppnår en konsentrasjon av salter som vanligvis ligger omkring 48 og 55$> fortrinnsvis omkring 52%. Denne konsentrerte opplosning oppblandes deretter med en polyfosfatblanding av kalium- og natriumsalter av samme type, og denne samlede blanding behandles deretter i en brennerovn eller kalsineringsovn, hvori torking og brenning av de blandede polyfosfatsalter av natrium og kalium foretas. Under kalsineringen holdes en temperatur på mellom 25O og 500°C og fortrinns- Preferably, this calcination step is carried out with the return of a part of the finished product to the previous treatment, as follows: The liquid from the third step is first evaporated in a multi-stage evaporator until a concentration of salts is reached which is usually around 48 and 55$> preferably around 52 %. This concentrated solution is then mixed with a polyphosphate mixture of potassium and sodium salts of the same type, and this combined mixture is then treated in a burner or calcining furnace, in which drying and burning of the mixed polyphosphate salts of sodium and potassium is carried out. During the calcination, a temperature of between 250 and 500°C is maintained and preferably
vis på omkring 300°C, og behandlingstiden ligger på omkring 1 time. show at around 300°C, and the treatment time is around 1 hour.
Det ligger åpenbart innenfor oppfinnelsens ramme å foreta dette femte trinn i fremgangsmåten på en hvilken som helst kjent måte. Det er således mulig å inndampe til torrhet den delvis konsentrerte opplosning med.48 til 55%'s saltinnhold, f.eks. i en dyseforstover, hvoretter produktet brennes i en kalsineringsovn eventuelt etter fukting av det torre, forstovede produkt. It is obviously within the scope of the invention to carry out this fifth step in the method in any known way. It is thus possible to evaporate to dryness the partially concentrated solution with 48 to 55% salt content, e.g. in a nozzle atomizer, after which the product is burned in a calcining oven, possibly after moistening the dry, atomized product.
Man går heller ikke utenfor oppfinnelsens ramme om man etter oppkonsentrering av væskene utsetter disse for en rensebehandling, som f.eks. filtrering, i den hensikt å fjerne de siste spor av faste for-urensninger som er utfelt i lopet av konsentreringen. You also do not go outside the scope of the invention if, after concentrating the liquids, you subject them to a cleaning treatment, such as e.g. filtration, with the aim of removing the last traces of solid impurities that have precipitated during the concentration.
De blandede polyfosfatsalter av natrium og kalium fremstilt i henhold til oppfinnelsens fremgangsmåte kan utsettes for ytterligere behandling bestående av en knusing, eventuelt forbundet med en granu-lering. The mixed polyphosphate salts of sodium and potassium produced according to the method of the invention can be subjected to further treatment consisting of a crushing, possibly associated with a granulation.
Fremgangsmåten kan utfores ved at det i forste trinn i denne . prosess anvendes en uren opplosning av fosforsyre, som spesielt kan komme fra fremstilling av fosforsyre ad våt vei. Når det f.eks. anvendes en fosforsyre som ikke er defluorert, danner det seg i lopet av det forste fremstillingstrinn en utfelling inneholdende fluosilikater av alkalimetaller, hvilke fraskilles fra væsken sammen med kalsiumsulfat under annet trinn av oppfinnelsens fremgangsmåte. Det er faktisk fordelaktig under forste trinn til å begynne med å innfore i reaksjonsblandingen en mengde natriumsulfat som er tilstrekkelig til å utfelle det tilstedeværende fluor, idet man etter fraskilling av det dannede natrium-fluosilikat fortsetter den beskrevne utforelse med tilsetning av kaliumsulfat. The procedure can be carried out in that in the first step of this . process, an impure solution of phosphoric acid is used, which can in particular come from the production of phosphoric acid by wet means. When it e.g. if a phosphoric acid that is not defluorinated is used, a precipitate containing fluosilicates of alkali metals is formed in the course of the first production step, which are separated from the liquid together with calcium sulfate during the second step of the method of the invention. It is actually advantageous during the first step to initially introduce into the reaction mixture an amount of sodium sulphate which is sufficient to precipitate the fluorine present, and after separation of the sodium fluosilicate formed, the described procedure is continued with the addition of potassium sulphate.
I henhold til en annen utforelse av fremgangsmåten er det mulig å fjerne fullstendig de foreliggende sulfationer i opplosningen fra annet trinn, ved i beregnede mengder å tilsette et bariumsalt som f.eks. bariumkarbonat, hvoretter det utfelte bariumsulfat fraskilles enten i et selvstendig trinn eller under filtreringen i fjerde trinn. According to another embodiment of the method, it is possible to completely remove the sulfate ions present in the solution from the second step, by adding calculated amounts of a barium salt such as e.g. barium carbonate, after which the precipitated barium sulphate is separated either in an independent step or during the filtration in the fourth step.
Den beskrevne fremgangsmåte frembyr, sammenlignet med tidligere fremgangsmåter, flere viktige fordeler: Metoden tillater bruk av råmaterialer som kan anvendes med særlig fordel, som eksempelvis naturlig fosfat, kaliumsulfat, samt eventuelt fortynnede og ikke rensede opplosninger av fosforsyre. Fremgangsmåten har ennå en stor fordel deri, at den kan utfores helkontinuerlig, og i at det ikke oppstår problemer med korrosjon. De fremstilte produkter har videre den fordel at de er lite hygroskopiske og lett går i opplosning. De fremstilte oppløsninger er stabile og denne stabilitet oker saltenes anvendelsesområde, særlig når det gjelder ut-lutende og kompieksdannende sammensetninger. The described method offers, compared to previous methods, several important advantages: The method allows the use of raw materials that can be used with particular advantage, such as natural phosphate, potassium sulfate, as well as possibly diluted and unpurified solutions of phosphoric acid. The method still has a major advantage in that it can be carried out completely continuously, and that no problems with corrosion arise. The manufactured products also have the advantage that they are not hygroscopic and dissolve easily. The prepared solutions are stable and this stability increases the salts' range of application, particularly when it comes to leaching and complex-forming compositions.
Nedenfor beskrives fem eksempler på utforelsen i henhold til oppfinnelsens fremgangsmåte. Five examples of the embodiment according to the method of the invention are described below.
Eksempel 1 Example 1
Dette eksempel vedrorer en kontinuerlig fremstilling av et blandet tripolyfosfatsalt av natrium og kalium, som i det vesentlige tilsvarer formelen Na0 [-Kn r-Po0nn. This example relates to a continuous preparation of a mixed tripolyphosphate salt of sodium and potassium, which essentially corresponds to the formula Na0 [-Kn r-Po0nn.
3o J->-> 3 10 3o J->-> 3 10
I en beholder med volum 60 m-' og utstyrt med roreverk innfores 10 m^/time av en opplosning av defluorert fosforsyre inneholdende 30 vektsprosent ^2^5' ^ tonn/time fosfatmineral "Maroc 75" i knust tilstand og 3 tonn/time vannfri kaliumsulfat. Reaksjonsblandingen holdes på omkring 50°C ved hjelp av luftgjennomblåsning. In a container with a volume of 60 m-' and equipped with an agitator, 10 m^/hour of a solution of defluorinated phosphoric acid containing 30% by weight of ^2^5'^ ton/hour phosphate mineral "Maroc 75" in crushed state and 3 tons/hour are introduced anhydrous potassium sulfate. The reaction mixture is kept at around 50°C by means of air blowing.
I den kontinuerlige prosess sorger man for å bibeholde det samme vektforhold mellom reaktantene som de opprinnelig ble innfort i. In the continuous process care is taken to maintain the same weight ratio between the reactants in which they were originally introduced.
Den dannede reaksjonsgrot filtreres kontinuerlig gjennom et vakuum-trommelfilter, og-filterkaken, som vesentlig består av kalsiumsulfat, vaskes med en liten mengde vann. The formed reaction slurry is continuously filtered through a vacuum drum filter, and the filter cake, which essentially consists of calcium sulphate, is washed with a small amount of water.
Det således oppnådde filtrat innfores sammen med vaskevannet The filtrate thus obtained is introduced together with the wash water
i en beholder med volum 10 m^. I denne beholder innfSres likeledes 1,65 tonn/time vannfritt natriumkarbonat. Reaksjonsblandingen, som oppviser et forhold K + Na på omkring 1, holdes ved ca. 70°C ved hjelp av en dampspiral. p Den fremstilte grot overfores gjennom overlop til en annen beholder med volum på 10 m^ og som likeledes holdes på en temperatur omkring 70°C, hvori innfores 2,25 tonn/time vannfritt natriumkarbonat. in a container with a volume of 10 m^. 1.65 tonnes/hour of anhydrous sodium carbonate is also introduced into this container. The reaction mixture, which exhibits a K + Na ratio of about 1, is maintained at approx. 70°C using a steam coil. p The prepared groat is transferred through an overflow to another container with a volume of 10 m^ and which is likewise kept at a temperature of around 70°C, into which 2.25 tonnes/hour of anhydrous sodium carbonate is introduced.
Den således fremstilte grot overfores igjen gjennom overlop The grot produced in this way is transferred again through the overflow
til et kontinuerlig vakuumfilter i den hensikt å fraskille de faste to a continuous vacuum filter in order to separate the solids
■forurensninger som i det vesentlige stammer fra fosfatmineralet (forbindelser av kalsium, jern, aluminium og magnesium). Filterkaken vaskes med vann og vaskevannene fores tilbake til den forste beholder med volum på 10 m^.. ■pollution which mainly originates from the phosphate mineral (compounds of calcium, iron, aluminum and magnesium). The filter cake is washed with water and the wash water is returned to the first container with a volume of 10 m^..
Deretter inndampes det resulterende filtrat fra sistnevnte operasjon inntil man oppnår et saltinnhold på 52 vektsprosent. The resulting filtrate from the latter operation is then evaporated until a salt content of 52% by weight is obtained.
Denne konsentrerte opplosning blandes med omtrent 6 deler ferdig produkt som resirkuleres, og den således fremstilte pasta kalsineres i en brennerovn eller kalsineringsovn av dreierortypen ved direkte oppvarmning, hvori produktets temperatur ved fullendt kalsi- This concentrated solution is mixed with approximately 6 parts of finished product which is recycled, and the paste thus produced is calcined in a burner or rotary kiln type calcining furnace by direct heating, in which the temperature of the product at complete calcination
nering er ca. 300°C. nering is approx. 300°C.
Det oppnås ca. 8 tonn/time av polyfosfat, som er ferdig kalsi-nert, og dette utgjor da, etter nedkjoling og knusing, det ferdige produkt, og resten kjores tilbake til trinnet for kalsineringstrinnet som beskrevet. It is achieved approx. 8 tonnes/hour of polyphosphate, which has been calcined, and this then, after cooling and crushing, forms the finished product, and the rest is driven back to the step for the calcination step as described.
Eksempel 2 Example 2
Dette eksempel vedrorer den kontinuerlige fremstilling av.et blandet tripolyfosfatsalt av natrium og kalium, hvilket i det vesentlige tilsvarer formelen Na0 r-K0 r-Po0-,n. This example relates to the continuous production of a mixed tripolyphosphate salt of sodium and potassium, which essentially corresponds to the formula Na0 r-K0 r-Po0-,n.
2,5 2,5 3 10 2.5 2.5 3 10
Det arbeides med de samme betingelser som under eksempel 1, men med den forskjell at det forste trinn av den partielle noytralisasjon i den forste beholder med volum på 10 m-^ utfores med 1,40 tonn/time vannfri kaliumkarbonat og 0,50 tonn/time vannfri natriumkarbonat. (I stedet for 1,65 tonn/time av vannfri natriumkarbonat alene). Work is carried out under the same conditions as under example 1, but with the difference that the first stage of the partial neutralization in the first container with a volume of 10 m-^ is carried out with 1.40 tonnes/hour anhydrous potassium carbonate and 0.50 tonnes/hour hour anhydrous sodium carbonate. (Instead of 1.65 tonnes/hour of anhydrous sodium carbonate alone).
På denne måte oppnås omkring 8,25 tonn/time blandet tripolyfosfatsalt av natrium og kalium, hvor det molekylære forhold mellom natrium og kalium er omtrent lik 1. In this way, around 8.25 tonnes/hour of mixed tripolyphosphate salt of sodium and potassium are obtained, where the molecular ratio between sodium and potassium is approximately equal to 1.
Eksempel 3 Example 3
Dette eksempel angår en kontinuerlig fremstilling av et blandet tripolyfosfat av natrium og kalium, som i det vesentlige til- This example concerns a continuous production of a mixed tripolyphosphate of sodium and potassium, which essentially
svarer formelen Nan r-K0 ,-Po0nr,. corresponds to the formula Nan r-K0 ,-Po0nr,.
l>5 3>5 3 10 l>5 3>5 3 10
Det arbeides igjen under de samme generelle betingelser som beskrevet i eksempel 1, men med den forskjell at den forste del av den partielle noytralisasjon i forste beholder med volum på 10 m<J> foretas med 2,2 tonn/time av vannfri kaliumkarbonat og annet trinn i den annen beholder med volum på 10 m-^ foretas med 0,65 tonn/time vannfri kaliumkarbonat, og 1,7 tonn/time vannfri natriumkarbonat. (I stedet for 1,65 tonn/time og 2,25 tonn/time vannfri natriumkarbonat respektivt). Work is again carried out under the same general conditions as described in example 1, but with the difference that the first part of the partial neutralization in the first container with a volume of 10 m<J> is carried out with 2.2 tonnes/hour of anhydrous potassium carbonate and other step in the second container with a volume of 10 m-^ is carried out with 0.65 tonnes/hour of anhydrous potassium carbonate, and 1.7 tonnes/hour of anhydrous sodium carbonate. (Instead of 1.65 tonnes/hour and 2.25 tonnes/hour anhydrous sodium carbonate respectively).
Man får på denne måte 8,5 tonn/time blandet tripolyfosfatsalt av natrium og kalium, som i det vesentlige tilsvarer formelen Na-^ ^K^ ^^O-^q. In this way, 8.5 tonnes/hour of mixed tripolyphosphate salt of sodium and potassium are obtained, which essentially corresponds to the formula Na-^ ^K^ ^^O-^q.
Eksempel 4 Example 4
Eksemplet angår kontinuerlig fremstilling av blandet pyrofos-fat av natrium og kalium, som. tilsvarer formelen Na<gKgP>gOy. The example relates to the continuous production of mixed pyrophosphate of sodium and potassium, which. corresponds to the formula Na<gKgP>gOy.
Man arbeider med de samme betingelser som angitt i de tidligere eksempler, med den forskjell at den forste del av den partielle nøytra-lisering i den forste beholder med volum på 10 m^ foretas med 3>5 tonn/ time kalilut inneholdende 50 vektsprosent K0H, og det annet trinn i One works with the same conditions as indicated in the previous examples, with the difference that the first part of the partial neutralization in the first container with a volume of 10 m^ is carried out with 3>5 tonnes/hour of kalilut containing 50% by weight K0H, and the second step i
den andre beholder med volum på 10 m-^ foretas med 5 tonn/time natron- the second container with a volume of 10 m-^ is made with 5 tonnes/hour of sodium
lut inneholdende 50 vektsprosent NaOH, i stedet for 1,65 tonn/time og 2,25 tonn/time med natriumkarbonat vannfritt, respektivt. lye containing 50% by weight NaOH, instead of 1.65 tonnes/hour and 2.25 tonnes/hour of anhydrous sodium carbonate, respectively.
På denne måte utvinnes 9 tonn/time blandet pyrofosfatsalt av In this way, 9 tonnes/hour of mixed pyrophosphate salt is extracted
natrium og kalium, som tilsvarer ovenstående formel Na2<K2P20y.>sodium and potassium, which corresponds to the above formula Na2<K2P20y.>
Eksempel 5 Example 5
Dette eksempel vedrorer en diskontinuerlig fremstilling av et This example concerns a discontinuous representation of a
blandet tripolyfosfatsalt av natrium og kalium, som tilsvarer i det vesentlige formelen Na0 r-K0 cPn0lri. mixed tripolyphosphate salt of sodium and potassium, corresponding essentially to the formula Na0 r-K0 cPn0lri.
2,5 2,5 3 10 2.5 2.5 3 10
I en beholder med volum I50 m^ og utstyrt med roreverk inn- In a container with a volume of 150 m^ and equipped with an agitator in-
fores 120 m- 5 av en defluorert fosforsyreopplosning inneholdende 30% 120 m-5 of a defluorinated phosphoric acid solution containing 30% is fed
^2^5' ve<^ en temPera't;ur på 50°C. I lopet av 1 time tilsettes 8 tonn knust fosfatmineral av typen "Maroc 75", °S derpå i lopet av en på- ^2^5' ve<^ a temPera't;ur of 50°C. In the course of 1 hour, 8 tonnes of crushed phosphate mineral of the "Maroc 75" type are added, °S then in the course of an
folgende time 10 tonn vannfri kaliumsulfat. Etter 6 timers reaksjons- the following hour 10 tonnes of anhydrous potassium sulphate. After 6 hours of reaction
tid filtreres den resulterende reaksjonsgrot gjennom rekker av filter- time, the resulting reaction slurry is filtered through rows of filter
presser, og filtratet samt vaskevannene fores inn i et lagringskar. presses, and the filtrate and the washing waters are fed into a storage vessel.
Man kan gjennomfore to slike operasjoner etter hverandre pr. dag. You can carry out two such operations one after the other per day.
Tredjedelen av den således fremstilte væske fra den foregå- The third part of the thus produced liquid from the previous
ende operasjon innfores deretter i en beholder med volum 70 m^, hvori etter hvert tilsettes 10,5 tonn'kaliumkarbonat og 10 tonn natriumkar- end operation is then introduced into a container with a volume of 70 m^, into which 10.5 tonnes of potassium carbonate and 10 tonnes of sodium carbonate are gradually added
bonat. Reaksjonsblandingen varmes p c rogressivt til 70 oC, og deretter til koking ved slutten av operasjonen, ved hjelp av en hetespiral med damptilforsel. Bonnet. The reaction mixture is heated progressively to 70 oC, and then to boiling at the end of the operation, using a heating coil with steam supply.
Den resulterende grot filtreres gjennom et batteri med filter- The resulting slurry is filtered through a battery of filter-
presser. Reaksjonen tar ca. 4 timer og det utfores 6 operasjoner av denne type pr. dag. presses. The reaction takes approx. 4 hours and 6 operations of this type are carried out per day.
Den filtrerte væske oppkonsentreres til et torrstoffinnhold The filtered liquid is concentrated to a solids content
på 50 vektsprosent. Etter rensing gjennom en filterpresse og en mellom- of 50 percent by weight. After purification through a filter press and an intermediate
.liggende lagringsperiode, for dette nye filtrat, inndampes væsken til torrhet i et spray-tårn (atomizer). Det fremstilte faste produkt behandles deretter i en kalsineringsovn med oppvarmning til 400°C. . lying storage period, for this new filtrate, the liquid is evaporated to dryness in a spray tower (atomizer). It produced solid product is then treated in a calcining furnace with heating to 400°C.
På denne måte fremstilles i middel l80 tonn/dag av et blandet tripolyfosfatsalt av natrium og kalium, i det vesentlige tilsvarende formelen Na0 r-K0 CP~0 In this way, an average of 180 tonnes/day is produced of a mixed tripolyphosphate salt of sodium and potassium, essentially corresponding to the formula Na0 r-K0 CP~0
2,5 2,5 3 10 2.5 2.5 3 10
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8300124A SE8300124D0 (en) | 1983-01-12 | 1983-01-12 | WOOD TIP TREATMENT |
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| NO834751L NO834751L (en) | 1984-07-13 |
| NO157828B true NO157828B (en) | 1988-02-15 |
| NO157828C NO157828C (en) | 1992-06-04 |
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| JP (1) | JPS59137583A (en) |
| AU (1) | AU567139B2 (en) |
| CA (1) | CA1216709A (en) |
| DE (1) | DE3346528A1 (en) |
| FI (1) | FI76843C (en) |
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| SE451605B (en) * | 1983-06-27 | 1987-10-19 | Mo Och Domsjoe Ab | PROCEDURE AND DEVICE FOR PROCESSING LIGNOCELLULOSAMATERIAL |
| US9091073B2 (en) * | 2012-12-10 | 2015-07-28 | Brad Wells | Method and apparatus for temporary surface protection |
| WO2015196285A1 (en) * | 2014-06-25 | 2015-12-30 | 9274-0273 Québec Inc. | Process and apparatus for treating lignocellulosic material |
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| CA1094263A (en) * | 1975-09-18 | 1981-01-27 | Douglas Atack | Method of producing ultra high yield pulp |
| US4211605A (en) * | 1978-08-03 | 1980-07-08 | Canadian International Paper Company | High yield chemimechanical pulping processes |
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1983
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1984
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| FI834877A (en) | 1984-07-13 |
| NO834751L (en) | 1984-07-13 |
| JPS59137583A (en) | 1984-08-07 |
| FI834877A0 (en) | 1983-12-30 |
| FR2539155A1 (en) | 1984-07-13 |
| SE8300124D0 (en) | 1983-01-12 |
| DE3346528C2 (en) | 1993-03-18 |
| FI76843B (en) | 1988-08-31 |
| FI76843C (en) | 1988-12-12 |
| CA1216709A (en) | 1987-01-20 |
| FR2539155B1 (en) | 1986-05-23 |
| NO157828C (en) | 1992-06-04 |
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