Patent Application
20180112355
Our present invention relates to an improved polysulfide production process wherein a specific second filtration process is installed before the polysulfide reactor.
Several different methods are known for producing polysulfide cooking liquor to be used in kraft cooking of pulp. They all relate to 4 different ways of forming polysulfide, i.e. a) adding electricity and white liquor to a electrolytic cell; or b) feeding clarified white liquor, oxygen and sodium hydrogen sulfide to a reactor filled with activated carbon catalyst particles, and c) feeding unclarified white liquor with a high content of catalyst particles, often lime mud particles, through a reactor fed oxygen or air, where the particles are used as catalyst, followed by clarification after the reactions, and finally d) addition of elemental sulfur.
Some old methods also expose the white liquor to heat and pressure, while transforming the sulfide content to polysulfide, with or without addition of some kind of catalyst that could be black liquor or lime mud particles that may be present in the white liquor or manganese oxide additive. Using the particle content in the white liquor as catalyst is disclosed in; a) U.S. Pat. No. 5,082,526 where presence of lime mud particles is used as catalyst, and b) U.S. Pat. No. 5,993,601, where presence of green liquor particles is used as catalyst.
Natural increase of polysulfide content may also be obtained after extended storage, as shown in EP1356156, but in opposition shown to be anticipated from old examples utilizing the residual content of black liquor acting as catalyst during storage.
Further, polysulfide increase in the white liquor may also be obtained using electrolytic cells, and U.S. Pat. No. 3,849,278 disclose one such embodiment.
One known method is the Moxy, Mead oxidation process, developed by Mead and further developed by Mitsubihisi Paper and Chiyoda, wherein active carbon is used as catalyst in the polysulfide reactor and disclosed in an early U.S. Pat. No. 4,024,229. Variant of this concept are shown in; U.S. Pat. No. 4,162,187 where the active carbon is partly coated with PTFE.
U.S. Pat. No. 52,345,456 disclose a later version where off gases from black liquor is combusted and fed to the polysulfide reactor.
In a known polysulfide production process like the Chiyoda polysulfide process, the content of suspended solids in the white liquor is reduced from some 10-100 ppm and down to less than 5 ppm, all described in “A new polysulfide process giving benefits to kraft pulp mill”, R. Inaba; T. Matsumura; E. Watanabe; & B. Soehartomo, 1994 (all employees of Chiyoda). The Chiyoda polysulfide process has also been disclosed in
The filtering technique used has been a filter bed technique, where the white liquor pass through a bed of granular filter particles, most often small anthracite particles having an average size of 1-2 mm. The content in the white liquor of suspended solids is captured in the bed and the entire bed needs to be regenerated and the solids needs to be flushed out at regular intervals. However, the only available method has been to fluidize the entire content of the bed by introducing a wash liquor, conventionally the already filtered white liquor, and send the wash filtrate back to the causticizing plant with the content of solids washed out. This wash out step typically needs to be activated once or twice a day at least, and thus the availability of the process decrease as no filtered white liquor may be obtained during the wash out step, and further a substantial volume of already filtered white liquor is lost during this wash step as the wash liquid volume exceeds the volume of the filter and needs to be used at a displacement ratio well over 2 (relative free volume of filter). The wash white liquor flow is large and therefore needs to be stored in a buffer tank before being returned back to causticizers at a lower continuous flow. Further, high capacity pumps is also needed for establishment of a fluidizing effect in the entire filter body enabling a wash out of the captured solids, increasing both investment costs as well as operational costs. In addition the filter needs further regeneration requiring shutdowns for acid washing, thus increasing the unavailability of the overall polysulfide manufacturing system. This typically occurs 4-12 times per year.
For some processes it is of importance that the white liquor is free from any solids content that may plug the reactor if especially dense packed beds with active carbon is used, or if electrolytic cells are used that may soon get a layer of the solids on the electrodes and membranes.
Hence, while it has been known that the white liquor needs to be clarified and have low content of suspended solids, filtering techniques used in polysulfide production processes has been filter beds where the white liquor pass and the suspended solids are captured in the bed, requiring wash out processes that reduce availability of the process and reduce amounts of the polysulfide production volumes.
It is a primary object of the invention to obtain a white liquor oxidation process preferably used for a polysulfide production process where the necessary filtering of the white liquor ahead of the oxidation reactor is done such that the process could be essentially continuous, keeping interruption of the polysulfide generation process to a minimum while providing a clarity below that of the traditional method and thus increasing availability of the following process step. This improves the polysulfide formation process to give a stable and continuous process who is subjected to less temporary shut downs and emptying of the reactor, hence reducing the transient operations at start up and shut down before establishing a steady state chemical conversion process.
It is a secondary object of the invention to obtain a polysulfide production process where the availability of the process may be improved substantially. The need for buffer tanks is reduced as the process may be designed with a process capacity close to that of the requested nominal production of partly or completely oxidized white liquor (also called orange liquor or oxidized white liquor).
Still another object of this invention is to provide an improved polysulfide production process with less operational cost, as no high capacity pumps needs to be installed capable of fluidizing the entire bed, in which scaling formation is reduced and plant economy increased.
The invention is related to a method for producing an oxidized white liquor, preferably a polysulfide cooking liquor, for use in a kraft pulp mill which comprises the steps of:
(a) adding burnt lime to green liquor in a slaker and passing the liquor to a series of causticizing vessels;
(b) passing the causticized liquor from the causticizing vessels to a first filtering or clarification process obtaining an accept flow of white liquor with a first order of suspended solids measured in ppm in the accept flow of white liquor and a reject flow of lime mud;
(c) passing the accept flow of white liquor through a second filtering process obtaining a filtered white liquor with a second order of suspended solids measured in ppm, said second order of suspended solids being at least half the order as of the first order of suspended solids and below 5 ppm, and
(d) passing the filtered white liquor through a polysulfide reactor with addition of an oxygen containing gas for promoting conversion of sulfides to polysulfide.
The invention is characterized in that the second filter process is performed in an essentially continuously operating cross flow filter, where a permeate passing through cross flow filter elements in the cross flow filter forms the filtered white liquor before sending the filtered white liquor to the polysulfide reactor.
The expression an essentially continuously operating cross flow filter is used for a process where the filtering process has an availability in excess of 95%, and typically up to 98%. Even if acid cleaning may be needed for the cross filter, such an acid cleaning needs only some 30 minutes per day, i.e. 2% of the time, and needs only some 20 m3/year of acid for this cleaning process. The reason is that the membrane in the cross filter to be cleaned is thin and calcium carbonate particles are easily dissolved in acid.
The oxidation process may be used for producing an oxidized white liquor, preferably a polysulfide cooking liquor. In order to convert 99% of the sulfide content to thiosulfate, i.e. fully oxidized white liquor, is typically 4 times more oxygen needed for this conversion compared to an optimized concentration of polysulfide.
The usage of cross flow filters avoid all the disadvantages of granular filter beds that has been used up to date in polysulfide production processes of the Chiyoda process (described in
According to a preferred embodiment of the inventive method the cross flow filter used in the process is a ceramic filter body with an effective filter membrane thickness of 1-100 μm and with a pore size in the range of 0.1-10 μm in the filter membrane. The pore size and filter thickness of the filter membrane is a guarantee that the filter membrane maintains most of its filtering capacity over a longer period of time even if some particles may penetrate the filter membrane. The filter body may have a pore size exceeding that of the membrane by a factor of 5-20, and will allow unhindered passage for permeate once it has passed the membrane, and provides the mechanical strength of the membrane and the filter element as such.
Yet, the inventive method preferably make use of a polysulfide reactor in form of a catalytic reactor using a packed bed of active carbon as catalyst while adding oxygen to the catalytic process. This type of reactor is especially sensitive for blocking the flow paths of the white liquor due to particle content in the white liquor.
Alternatively, the inventive method preferably make use of a polysulfide reactor in form of an electrolytic cell. Also these electrolytic cells are sensitive for depositions on the cathode of the electrolytic cell due to particle content, i.e. calcium carbonate, in the white liquor. As the deposition increase in coverage and thickness over time the efficiency of the electrolytic cell drop in proportion to this order of deposition.
The inventive method also works in synergy with the preceding first filtering process if the first filtering process is done in a precoat filter, using the precoat as an active filter media to capture the calcium carbonate particles in the precoat. Precoat filter results in filtrates that contains very small amount of solids as the solids are captured in the precoat while offering a high production rate of clean filtrate per filter unit area.
In the inventive method is also the cross flow filters configured such that the cross flow filter elements are installed in at least 2 sets of cross flow filter elements. This improves the availability of the system and a continuous output of filtered white liquor as one set may be temporarily out of operation.
In an alternative configuration, at least 2 sets of cross flow filter elements are installed in series enabling use of only one single pump for circulating the retentate through the filters.
In yet an alternative configuration, at least 2 sets of cross flow filter elements are installed in parallel enabling availability of the system if one set is out of operation.
The above and other objects, features and advantages of the invention will become more readily apparent from the following description, reference being made to the figures in which:
Prior Art Process
In
The disadvantage with this conventional process is that the filter bed in filter F needs to be regenerated and all calcium carbonate particles captured in the bed needs to be removed in order to prevent the filter to become blocked over time.
The method of regeneration implemented is to wash the entire particle bed vigorously with the already filtered white liquor to such an extent that the entire particle bed is fluidized. This is done by starting pump P5 and opening valve V3, while closing valve V1, and introducing the pressurized white liquor into the bottom of the particle bed and flushing out the liquid via an open valve V4, while valve V2 is shut, with its content of calcium particles into a storage tank WaL-ACC capable of storing the entire volume of wash liquid used. Once the washing process is ended, the wash liquid used, with its content of calcium particles flushed out, is sent back to the process, and preferably before the first white liquor filter WLF. In order not to disturb the process, the wash liquid is returned as a small flow over an extended time.
The Inventive Process
The inventive process is shown in
In chemical engineering cross flow filtration is a type of filtration. Cross flow filtration is different from dead-end filtration in which the feed is passed through a membrane or bed, the solids being trapped in the filter and the filtrate being released at the other end. Cross-flow filtration gets its name because the larger part of the feed flow travels tangentially across the surface of the filter, rather than into the filter. The principal advantage of this is that the filter cake (which can blind the filter) is substantially washed away during the filtration process, increasing the length of time that a filter unit can be operational. It can be a continuous process, unlike batchwise dead-end filtration.
In
Now, this Cross flow filtration technique has been successfully implemented in green liquor filtration in Kraft pulp mills by CleanFlow AB, and the filtering body used with a membrane pore size of 0.1-10 μm, more preferred 0.1-5 μm and most preferred 0.2-1.0 μm, for the green liquor filtration application has been patented in SE,C,533833 (corresponds to pending EP,A,2414585).
In
In
Cleaning of the filter elements in the white liquor filtering process is relatively simple as the bulk content of particles in the already filtered white liquor is calcium carbonate that relatively easy dissolves in an acidic cleaning cycle.
The cleaning process could also be a simple backwashing of the membrane filters, pressurizing the white liquor on the permeate side such that a reversal of flow is obtained over the membrane filters.
The membranes may also be cleaned in place, or by disconnecting an individual filter body as disclosed in
In a specific implementation of the invention the cross flow filter system is designed for a nominal production of 420 m3/h filtered white liquor, using ceramic membrane filters with a pore size of approximately 0.3-0.8 μm. The white liquor filtered once before is obtained from a pressurized disc filter operating with a precoat of lime mud that reduce the content of lime mud particles in the white liquor to a level of 20 mg/l, i.e. this is thus the level of particles in the white liquor fed to the cross flow filters. The part of the retentate that is returned back to the causticizing vessels, preferably to last causticizing vessel ahead of the disc filter is, due to the recirculation and bleed off of permeate, experiencing an increase of the content of lime mud particles in the white liquor to a level of 1060 mg/l. The product liquor, i.e. the filtered white liquor has a very low content of lime mud particles, and in the mg/l scale less than 0 mg/l, and as measured in ppm well below 3 ppm. During normal operation varying in between 1-2 ppm. Compared with the nominal production of filtered white liquor, i.e. about 420 m3/h filtered white liquor, the recirculation rate through the filters is 2400 m3/h and the recirculated volume is pressurized to about 0.2-0.3 bar. The recirculation volume over the filters is thus in excess of 5.7 times that of the production volume of filtered white liquor
Above example is from a conventional causticizing plant with its specific lime recovery process, and the residual lime mud particle content in the white liquor may differ both in absolute level (mg/I or ppm) and in distribution of particle sizes, but cross flow filters may be modified using different pore sizes in the membrane adapted for the specific white liquor. However, the combination of a first filter and a subsequent cross flow filter reach astonishing low residual content of solids in the permeate. The reduction of particle content is especially important for the subsequent catalytic process in the polysulfide reactor, as this reactor may extend its availability at least 3-5 fold, before the active carbon bed is blocked, by reducing solids content in the white liquor from 5 ppm and down to 1 ppm. A similar positive effect is also obtained if the polysulfide conversion is done in an electrolytic cell, where deposits may be formed on the cathode depending on residual content of solids.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1550427-7 | Apr 2015 | SE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SE2016/050276 | 4/1/2016 | WO | 00 |
