Paper is widely used worldwide in commerce and in homes and has a variety of uses. Pulp making is thus carried out on a large industrial scale worldwide to produce sufficient quantities of paper. Accordingly it is highly desirable that such pulp making operations be carried out in a cost effective, efficient operation with minimum manufacturing equipment downtime and minimum periods of reduced pulp making process equipment efficiency.
The basic steps in industrial pulp making are to convert plant fiber into chips, convert chips into pulp, (optionally) bleach the pulp, wash the pulp, and transform the pulp into suitable paper which can be used in paper products such as writing paper, newsprint and paper for documents.
Typically, several chemical pulping processes are used in industrial pulp making operations. Well known industrial alkaline chemical pulping processes include the Kraft (or sulfate), soda and alkaline sulfite processes. The Kraft process makes the strongest fibers of any pulp producing process and is the most commonly used pulp making process in part due to its efficient recovery process for the cooking chemicals. While the present invention has applicability to any of the above alkaline chemical pulping processes, it is particularly useful with the Kraft process and, as such, the Kraft process is described in more detail below.
Initially, suitable trees are harvested, debarked and then chipped into suitable size flakes or chips. These wood chips are sorted with the small and the large chips being removed. The remaining suitable wood chips are then charged to a digester (which is a vessel or tank for holding the chips and an aqueous digesting composition, such tanks can be designed for either batch or continuous operation).
Illustratively, in a batch type digester, wood chips and a mixture of “weak black liquor,” the spent liquor from a previous digester cook, and “white liquor,” a solution of sodium hydroxide and sodium sulfide, that is either fresh or from the chemical recovery plant, is pumped into the digester. In the cooking process lignin, which binds the wood fiber together, is dissolved in the white liquor forming pulp and black liquor.
The digester is sealed and the digester composition is heated to a suitable cook temperature under high pressure. After an allotted cooking time at a particular temperature and pressure (H-factor) in the digester, the digester contents (pulp and black liquor) are transferred to a holding tank. The pulp in the holding tank is transferred to brown stock washers while the liquid (black liquor formed in the digester) is sent to the black liquor recovery area, i.e. black liquor evaporators. The black liquor is evaporated to a high solids content, usually 60–80% solids, using a multiple effect evaporator, for example. The higher the solids content, the more difficult it is to pump the black liquor and the more scale problems the pulp mill will have. One of the most troublesome is calcium carbonate scale which forms in various areas of the pulp mill, including the digester, the black liquor evaporator area, and the brown stock washing area.
Most commercial paper mills use multiple effect evaporators (MEE) as the black liquor evaporators. These evaporators generally range from four to eight effects in length. Generally, undesirable calcium carbonate scaling occurs in only one or two effects. Currently, most mills do not use any scale inhibitor but rather contend with the scale problem by shutting down the black liquor evaporator section and washing out the calcium carbonate scale with hot acid, i.e. acid cleaning. This hot acid boil out adversely affects papermill production and is a concern because the acid used is corrosive to mill piping and equipment.
The Kraft cook is highly alkaline, usually having a pH of 10 to 14, more particularly 12 to 14. The digester composition contains a large amount of sodium sulfide, which is used as an accelerant to increase the delignification rate of the cook. This works to release the lignin in the wood chips and thus the cellulose becomes available as pulp.
The combination of operating conditions in the Kraft process is conducive to scale formation and deposition and increases the propensity of the calcium carbonate scale to form, deposit and adhere to metallic and other surfaces within which it comes in contact. Under such process conditions, calcium present in the water and leached from the wood in the Kraft process can react with carbonate and produce rather rapid scaling with the deposition of calcium carbonate scale. Such scale is frequently deposited in the digester, piping, heat exchangers etc., all of which have surfaces on which the calcium carbonate can deposit and adhere. Such deposition builds up over time and can result in undesirable premature shutdowns downstream on the pulp making manufacturing line to remove scale deposits by hot acid washing.
Several patents and a technical article disclose problems of scaling. In “An Effective Sequestrant For Use In Controlling Digester Scale,” R. H. Windhager, Paper Trade Journal, pp. 42–44, Nov. 5, 1973, the use of small quantities of mono-aminomethylene phosphonic acid (ATMP) as a calcium carbonate scale inhibitor in a digester to inhibit scale deposition from the digester cooking liquor is disclosed.
U.S. Pat. No. 4,799,995 (issued to Druce K Crump et al. on Jan. 24, 1989) discloses that inhibition of calcium scale under conditions found in pulp digesters has been accomplished by employing mixtures of polyamino(polyalkylenephosphonic) acids with non-ionic surfactants added to the pulp liquor. This U.S. patent also discloses that phosphonates such as nitrilotris(methylenephosphonic acid) (“NTMP” or “ATMP”), 1-hydroxyethane-1,1-diphosphonic acid (“HEDP”) and sodium 1-hydroxyethane-1,1-diphosphonate (“NaHEDP”) are said to have been commonly used to control scale. However, the '995 patent discloses that the use of HEDP in black liquor actually promoted scale and use of diethylenetriamine penta(methylenephosphonic acid) (“DTPMP”) in black liquor without the presence of a nonionic surfactant resulted in only limited scale reduction. While the '995 patent discloses the use of nonionic surfactants to improve scale reduction, it is preferred to avoid the use of surfactants in chemical pulp processes, particularly in the digester. The compositions of the present invention when added to an alkaline chemical pulp process digester are effective at inhibiting calcium salt scale in chemical pulp processes without the need for a nonionic surfactant.
Canadian Patent No. 1,069,800 (Philip S. Davis et al., Jan. 15, 1980) discloses the addition of blends of organophosphonates, e.g. 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), with amino-organo phosphonates, e.g. amino tri(methylenephosphonic acid) (AMP), ethylenediamine tetra(methylenephosphonic acid) (EDTPA) and hexamethylenediamine tetra(methylenephosphonic acid) (HMDTA), to black liquor to reduce calcium carbonate scale in a black liquor evaporator system at a pH above 9. This patent also discloses that use of individual (single) phosphonates, instead of the disclosed blends, were not effective at a pH above 9 to inhibit calcium carbonate crystallization.
U.S. Pat. No. 4,851,490 (issued to Fu Chen et al. on Jul. 25, 1989) discloses water soluble polymers containing hydroxyalkyleneaminoalkylene phosphonate functions which are said to have utility as deposit control agents effective in a number of water systems such as cooling, boilers, conversion coating, paper and pulp processing and gas scrubbing.
U.S. Pat. No. 5,534,157 (issued to Craig D. Iman et al. on Jul. 9, 1996) discloses a method for inhibiting the formation, deposition and adherency of scale-forming salts in process waters at high pH utilizing polyether polyamine methylene phosphonates. At column 4, lines 35–51 thereof, this U.S. patent discloses that inhibitors such as HEDP and ATMP are useless as scale inhibitors at alkaline pH conditions.
U.S. Pat. No. 5,562,830 (issued to Davor F. Zidovec et al. on Oct. 8, 1996) discloses a method of inhibiting corrosion and scale formation and deposition in aqueous systems by adding a combination of a polyepoxysuccinic acid or salts thereof and a phosphonocarboxylic acid or salts thereof.
U.S. Pat. No. 5,552,018 (issued to Johan Devenyns on Sep. 3, 1996) discloses a process in which a peroxyacid is employed to improve the selectivity of the delignification of a chemical paper pulp that has already undergone a delignifying treatment in the presence of chemical reagents, i.e. a Kraft cook. Phosphonates are disclosed as stabilizers in this process.
Despite the aforementioned patents and technical article, enhanced methods and compositions for inhibiting the formation, deposition and adherence of scale to metallic surfaces particularly in commercial chemical pulp processing equipment is highly desired.