GB1595928A - Method and apparatus for sulphonation of resinous articles - Google Patents

Description

(54) METHOD AND APPARATUS FOR SULFONATION OF RESINOUS ARTICLES (71) We, THE KARTRIDG PAK CO., a Corporation organised and existing under the laws of the State of Iowa, United States of America, having its principal place of business at 807, West Kimberly Road, Davenport, Iowa 52808, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates generally to an improved method and apparatus for surface treating resinous articles, being especially suitable for the sulfonation treatment of the interor of polyethylene containers in order to significantly improve their impermeability, thereby rendering them suitable for use as storage containers of low polarity organic chemicals. The invention is particularly useful in treating vehicle gasoline tanks so they may be constructed of light weight resins rather than metals, which resins would otherwise not be suitably impermeable to gasoline.

It is known from publications such as US Patents No. 3,613,957 and No. 3,740,258 that a sulfonation treatment of the interior of resinous enclosure members will quite significantly improve the ability of those containers to hold organic chemicals for extended periods of time while avoiding any significant losses thereof, the disclosure of these patents being herein incorporated-by reference. Prior publications, such as those of these patents. while fully disclosing the chemical principles involved in the present invention, teach the use of sensitive gas analysis and control equipment for producing a desired percentage composition of sulfur trioxide in dry air. Generally, these systems do not easily and conveniently form these compositions but require a stream of dry air saturated with sulfur trioxide with a variable stream of dry air.

Various other publications show an apparatus for treating resinous containers with certain gas mixtures to improve their barrier resistance to solvents and gases. Some such publications for example US Patent No 3,998,180 describe a system having a single treatment station for carrying out the necessary gas introduction and exhaustion steps. A system having a single treatment station is not particularly useful for production line operations where short times and multiple treatment facilities are valued highly.

The present invention overcomes these disadvantages of previously disclosed sulfur trioxide treatment systems and avoids the low productivity associated with single treatment station systems.

It is concerned with a multi-station indexing system (and method) wherein however separate supply paths, and preferably separate exhaust paths, are provided for the sulfur trioxide-containing gas and the ammonia, respectively and a rotary manifold so arranged for supplying the gases respectively to appropriate ones of the various treatment stations through which the articles are indexed.

The present invention provides an apparatus for treating resinous articles with various gases, comprising: means having multiple platforms for loading resinous articles thereonto, having a rotary manifold for directing gases to said resinous articles at multiple treatment stations while avoiding mixing of gases which react with each other; means for indexing said multiple platforms sequentially around said rotary manifold from one treatment station to another, one of said treatment stations being for injecting a mixture of sulfur trioxide and dry air from a blending means, and another of said treatment stations being for injecting generally gaseous ammonia from a source thereof; a lower manifold for collecting gases that have been thus injected to said resinous articles at the said treatment stations; and exhaust means associated with said lower manifold.

The present invention provides also a method for treating resinous articles with various gases, comprising: loading a resinous article onto a platform of a rotary indexing multiple station treatment means; indexing said treatment means from treatment station to treatment station at which respective treatments occur; injecting to said resinous article a mixture of sulfur trioxide and dry air through a path from a blending means; exhausting the mixture as a substantial part thereof from the resinous article; injecting gaseous ammonia to said resinous article through a path different from said path of the sulfur trioxide blend; exhausting the ammonia and any remaining sulphur trioxide blend from said resinous article; and unloading said resinous article from said rotary indexing multiple station treatment means.

In a preferred embodiment the invention includes a blending system for liquid sulfur trioxide and dry air which is easily regulated by means of generally unsophisticated equipment that is easily and accurately monitored and operated by relatively untrained production workers. In a further one of the stations between the first-mentioned two stations, flushing air may be injected into the articles.

Furthermore, the exhausted gases may be neutralized in a hydrolysis scrubbing unit linked to the exhaust.

In the accompanying drawings: FIG. 1 is a flow diagram of a preferred total treatment system wherein the present invention may be practiced, including a blending means, a treatment means, and a scrubber means; FIG. 2 is a top plan view of the preferred means shown diagrammatically in FIG. I for blending liquid sulfur trioxide with an inert gas in precise concentration; FIG. 3 is a cross-sectional view through the blending means in FIG. 2; FIG. 4 is a top plan view of the preferred treatment means shown diagrammatically in FIG. I in which resinous containers, some being partially broken away, are loaded onto multiple stations of a rotary indexing module for communication with a rotary gas distribut ion manifold; FIG. 5 is a side elevational view of the treatment means of FIG. 4 from which all but one of the multiple treatment stations have been omitted; FIG. 6 is an assembled composite of selected vertical cross sections through the various assembly parts owt'the rotary manifold of FIGS. 4 and 5, showing structural details of the various assembly parts: FIG. 7 is a fragmentary sectional view taken along line 77 of FIG. 4 in which only treatment station No. I is shown and from which certain details are omitted for clarity; FIG. 8 is a fragmentary sectional view taken along line 8-8 of FIG. 4. in which only treatment station No. 2 is shown and from which certain details are omitted: FIG. 9 is a fragmentary sectional view taken along line 9--9 of FIG. 4, in which only treatment station No. 6 is shown and from which certain details are omitted; FIG. 10 is a fragmentary sectional view taken along line 1F10 of FIG. 4, in which only treatment station No. 7 is shown and from which certain details are omitted; and FIG. 11 is a fragmentary sectional view taken along line 1111 of FIG. 4, in which only treatment station No. 8 is shown and from which certain details are omitted.

FIG. I illustrates the blending means, generally indicated at li, the treatment means, generally referred to by 12, the scrubber means, generally designated as 13, and the preferred interconnections thereamong. fn blending means 11, liquid sulfur trioxide and dry air are mixed together at desired concentrations. Treatment means 12 directs the various treatment gases as required for improving the impermeability of resinous articles stationed thereon (FIG 4).

Scrubber means 13 neutralizes and scrubs the exhaust gases from the treatment means 12.

Blending means 11 includes one or more storage drums 14 containing liquid sulfur trioxide; a source of dry air which usually comprises an air compressor 15 and an air dryer 16; a heater 17; and one or more blending tanks 18 of known volume for mixing the sulfur trioxide and the dry, heated air. A valved conduit means 19 delivers the blend of sulfur trioxide and air to the treatment means 12. Ammonia gas is supplied to treatment means 12 from a supply means 20. After the various gases pass to the treatment means 12 and into contact with the resinous articles being treated thereon, the ammonia-containing gases are exhausted therefrom through a line 21, and the sulfur trioxide-containing gases are exhausted through a line 22. Each of lines 21 and 22 opens into a side chamber 23 of a mist eliminator 24 of the scrubber means 13. The S07 exhaust gases and the NH3 exhaust gases are brought together in the presence of an atomizing spray of water injected through a spray nozzle 25. At this point, the gases are hydrolyzed. They also neutralize each other, and the water vapour removes the heat of the chemical reaction.

The gases pass into a main chamber 26 of the mist eliminator 24, wherein heavier liquid particles drop down into a sump 27 in the lower portion of the mist eliminator 24 and wherein the gases pass upwards through a pair of atomizing spray nozzles 25a, 25b to complete the hydrolization and neutralization process. Next, the gases pass through a filter element 28 where any mists are removed, and a blower 28a exhausts the gases to atmosphere. An upper spray nozzle 25c is not used in normal operation, but only occasionally for clean-up purposes. Usually, each of the spray nozzles 25, 25a, 25b. and 25c will be assisted by a shop air supply 29 providing air under pressure of about 25 pounds per square inch. A sump overflow waste tank 30 maintains the sump 27 at a level below the spray nozzles 25a, 25b.

Details of the blending means 11 are shown in FIGS. 2 and 3 as well as in FIG. 1.

Preferably, blending means 11 includes two cylindrical blending tanks 18 which alternately charge, discharge, and recharge so as to provide a continuous supply of treatment gas to the treatment means 12. Liquid sulfur trioxide passes from storage drums 14 through valves 31 by means of a metering pump 32, a solenoid valve 33 and an atomizer 34, preferably discharging into the central portion of each blending tank 18. The metering pump 32 is usually a positive displacement pump which can be readily utilized to provide a measured amount of liquid sulfur trioxide into the tank 18.

The compressed and dried air leaving the air dryer 16 passes through a pressure regulator valve 35 to provide dry air at a predetermined constant pressure (usually in the order of about 40 pounds per square inch) after which the dry air under pressure passes through a solenoid valve 36 and into the heater 17. Heater 17 raises the dried, pressurized air to a predetermined temperature, usually on the order of 250"F. after which the air is passed through another solenoid valve 37 into the blending tank 18 through an injector 38. The preferred injectors 38, as shown most clearly in FIG. 2. impart a tangential motion to the entering heated gases, urging the gases to follow a path generally along the circumferential side wall of each blending tank 18 to create a cyclonelike action which allows additional heat to be transferred from the side walls of the tank and enhances the blending capabilities of blending means 11.

Figure 3 shows in greater detail a sulfur trioxide inlet line 41 for transporting the sulfur trioxide into the blending tank 18 through the atomizer 34. As shown, inlet line 41 preferably communicates with the heated air inlet line 42 in a manner that permits a small amount of heated dry air to blow the liquid sulfur trioxide through the atomizer 34. Atomizer 34 preferably directs the sulfur trioxide in generally radial directions within each tank 18 to facilitate the blending operation.

In the preferred embodiment shown, blending means 11 includes a heated and insulated cabinet 43 in order to assist in maintaining the desired conditions within the tanks 18. Tanks 18 will usually include temperature controls 44 and pressure controls 45 of known conventional type, and may also have band heaters 46 to provide additional heat for vaporization within tanks 18 and to maintain a predetermined uniform temperature within cabinet 43.

Structural details of the treatment means 12 are shown in FIGS. 4, 5 and 6. Treatment means 12 includes multiple platforms 51 at which an item to be treated such as a resinous gasoline tank 52 may be loaded for the purpose of introducing and withdrawing gases at specified times and in predetermined concentrations. The nine stations of the preferred means 12 are identified as treatment stations No. I to 9 on FIG. 4. Items or tanks 52 are loaded onto and unloaded from the treatment means 12 at station No. 9. At station No 1 dry air enters item 52a to flush out undesired gases, and at station No. 2 the air and sulfur trioxide blend from blending means 11 is injected into item 52b. No additional gases are injected into items 52c, 52d and 52e at stations No. 3, No.4, and No.

5. Item 52f at station No. 6 is subjected to a second dry air flush, and at station No.7 NH3 gas is injected into item 52g. An air flushing treatment is carried on at station No. 8 upon item 52h. When this preferred nine-station arrangement is used, the stations will be separated by about 40 , meaning that station No. 9 is at 0 or 360 , station No. 1 is at 40 , station No. 2 is at 80 , station No. 3 is at 120 , station No. 4 is at 160", station No. 5 is at 200 , station No. 6 is at 240O, station No. 7 is at 280 , and station No. 8 is at 320 .

Appropriate gases which enter each of stations No. 1, No. 2, No. 6, No. 7 and No. 8 pass through inlets 53, 54, 55, 56, and 57, respectively. Each of the air inlets 53, 55 and 57 communicates with air compressor 15 through conduit means 58 (FIG. 1). The sulfur trioxide mixture from blending tank 18 and valved conduit means 19 (FIG. 1) passes through inlet 54. Ammonia gas from the ammonia gas supply means 20 enters through inlet 56.

The individual platforms 51 of the treatment means 12 rotate, preferably in a clockwise direction, whereby each item 52 indexes from station No. 9 to station No. 1 and then to station No. 2 and so forth through to station No. 9, at which time the fully treated item 52 is unloaded from the treatment means 12. Referring to FIG. 5, each platform 51 indexes in response to an indexing drive plate 59, a rotary manifold 60 indexing along therewith. Treatment conduit 61 passes the dry air to item 52a at treatment station No. 1, passes the dry air and sulfur trioxide mixture to item 52b at station No. 2, and passes the dry air to item 52f at station No. 6. The other treatment conduit 62 supplies ammonia gas to item 52g at station No. 7 and supplies air to item 52h at station No. 8. The sulfur trioxide and the ammonia are thereby kept separate to prevent undesirable reactions between sulfur trioxide and ammonia.

Each treatment platform 51 communicates with a lower manifold, identified generally as 63, through an exhaust line 64 which terminates inside of an open trough 65. Trough 65 is annularly disposed within the lower manifold 63. Exhaust gases collect in the lower manifold 63 and pass out of the treatment means 12 through an exhaust line 66 or 67.

Preferably, two baffles or gates 68 and 69 are located within the lower manifold 63 to divide it into two separate compartments 71 72 (Fig. 4), and one exhaust line 66 opens into compartment 71, while the other exhaust line 67 opens into compartment 72. By this structure, separate exhaust means are provided for the sulfur trioxide-containing gases and for the ammonia-containing gases to thereby prevent undesirable mixing thereof.

For example, as shown in FIG. 4, compartment 71 extends from about 70 to about 250 , which includes stations No. 2, No. 3, No. 4, No. 5 and No. 6, meaning that the sulfur trioxide injected at station No. 2, after having treated the items at these stations, is free to collect within compartment 71 and be withdrawn therefrom by exhaust line 66, located at 210 . Correspondingly, compartment 72 extends from about 250 to about 70" and includes stations No. 7, No. 8, No.9 and No. I, meaning that the ammonia injected at station No. 7. after having treated the items at these stations. is free to collect within compartment 72 and be withdrawn therefrom by exhaust line 67, located at 320 .

With particular reference to FIG. 6, a vertical pipe 73 is below and communicates with the inlet 53 at station No. 1. Similar venical pipes 73a (FIG. 8) and 73b (FIG. 9) are so situated below both the inlet 54 at station No. 2 and the inlet 55 at station No. 6 respectively. The bottom end of each pipe 73 will communicate with one of the nine upper elbow bores 74 within the rotary manifold 60 as the stations are indexed. Upper elbow bores 74 in turn seat within the respective nine conduits 61, thereby providing a gas passageway between each of inlets 53. 54.

and 55 and the particular item 52 loaded onto stations No. 1, No. 2, and No. 6, respectively.

A vertical bore 75 through center post 76 provides a passageway for inlet 56 at station No. 7 to communicate with an L-shaped bore 77. A similar vertical bore 75a (FIG. I I) provides a passageway for inlet 57 at station No. X to L-shaped bore 77a. The top end of each bore 77 will communicate with one of the nine lower elbow bores 78 within the rotary manifold 60 as the stations are indexed. Lower elbow bores 78 in turn seat within the respective nine conduits 62, thereby providing a gas passageway between both of inlets 56 and 57 and the particular item 52 loaded onto stations No. 7 and No. 8, respectively.

FIG. 7 illustrates the communication which occurs at station No. 1, when dry air is injected into the item 52a. At station No. 1, this is the only gas-passing connection between an elbow bore 74, 78 and either a vertical pipe 73 or an L-shaped bore 77. FIG.

8 illustrates the communication at station No. 2, when the blend of sulfur trioxide and dry air is irtcted into the item 52b, this being the only station No. 2 gas-passing connection between an elbow bore 74, 78 and either a vertical pipe 73 or an L-shaped bore 77. FIG. 9 illustrates the only gas-passing connection at station No.6 between an elbow bore 74, 78 and either a vertical pipe 73 or an L-shaped bore 77, dry air being passed at this station. FIG. 10 illustrates the communication at station No. 7, when the ammonia gas is injected, this being the only station No. 7 gas communication between an elbow 74, 78 and either a vertical pipe 73 or an L-shaped bore 77. FIG. 11 illustrates the only gaspassing communication at station No. 8 between an elbow bore 74, 78 and either a vertical pipe 73 or an L-shaped bore 77, air being injected to items 52h at this station.

Each of these gas-injecting functions will be performed simultaneously on different ones of the various items 52ash which are loaded at the respective platform at any given time. the rotary manifold 60 thereby serving to distribute the desired gas to each of the designated stations. Should a platform not have an item 52 loaded thereon, then appropriate sensors (not shown) will prevent gas flow to such vacant platforms, the sensors allowing gas passage to occupied platforms.

Compressed shop air is provided to the rotary manifold 60 through a centrally located bore 81 having spoked bores 82 alignable with transverse bores 83 communicating with each station, whereby the compressed air actuates each treatment station and item or tank holding fixture, there also being provided a "no-item, no-treatment" air switch (not shown) at each treatment station.

Several timer controlled valves (not shown) serve to regulate the flow of gases into inlets 53, 54, 55, 56, and 57. These valves actuate during the dwell portion of the rotary cycle. By adjustment of the timers that actuate these valves, control of the amount of each gas passed through the inlets is achieved. Since each gas is pressure regulated. gas flow meters with a visual readout means enable the time settings to be readily converted to gas volumes.

The following exemplifies proceeding with the method in accordance with this invention. As a first stage, liquid sulfur trioxide and heated dry air are combined, the object being to form a blend having a concentration suitable for treating resinous articles to improve their impermeability, such concentrations usually being on the order of 15 mole per cent sulfur trioxide in dry air. Mole percentages of less than I per cent to greater than 20 per cent can be formed and used.

The desired concentration mixture is formed volumetrically at constant temperature without sophisticated controls. Basically, liquid sulfur trioxide is metered by stroking a pulse pump a preselected number of times into a closed vessel of known volume and temperature.

More particularly, in this first stage, a source of compressed air is dried, its pressure is regulated at a preselected pressure, such as 40 pounds per square inch. Greater pressures up to 60 or 70 pounds per square inch may be developed. The pressurized air is heated to a desired temperature, usually about 250cm., although temperatures as high as 300 or 350 F. are possible at the greater pressures.

That heated, pressurized air then flows into a tank of known volume to provide a known quantity of dry air. Into this quantity of dried air is sprayed a preselected volume of sulfur trioxide, the amount being regulated by positively displacing known volumes of the liquid sulfur trioxide and keeping track of the number of such displacements whereby the volume pumped and sprayed into the tank can be accurately determined. The formation of the desired mixture is enhanced by tangentially introducing the heated dry air to maximize the ability of the dry air to quickly heat the sprayed sulfur trioxide to the desired temperature for developing the desired treatment concentration.

In the next stage, the resinous items to be treated with the sulfur trioxide-air mixture are loaded onto a treatment means which indexes the items in a rotary fashion whereby each item at each particular indexing station of the treatment means is being subjected to a treatment step for which that station is designed. An item to be treated is first loaded onto a loading station. Then it is automati cally indexed by the indexing means to the next station at which time the operator will place another untreated item onto the loading station. This indexing continues from station to station while the items are treated as needed until each item makes a complete revolution back to the loading station at which time it will be removed.

In the preferred or exemplified method, a total of nine indexing steps rotate each resinous item through nine stations, as follows: The first step is one of flushing the item by injecting dry air. Then, at the second station. the sulfur trioxide-dry air mixture prepared in the first stage of this method is fed to the item. In the third, fourth and fifth stations. no additional gases are introduced, these stations being ones at which the sulfur trioxide proceeds to advantageously treat the item to improve its impermeability to organic chemicals. Excess gases are free to exhaust from the items at the second through fifth stations. The sulfur trioxide-gas mixture remaining is withdrawn at the sixth station where a second flushing step with dry air is effected. This is followed by treating the item with ammonia gas at the seventh station in order to properly neutralize the item that remains slightly acidified by residual sulfur trioxide. The ammonia gas is free to exhaust from the items at the seventh and eighth stations. At the eighth station the item is flushed with air in order to complete the removal of any residual ammonia gas before the item is removed at the ninth station, the loading station.

The exhaust gases from the second through sixth stations, which-include-sulfur trioxide, are kept separate from the exhaust gases from the seventh t-hrough eighth stations, which include ammonia gas. Each separate exhaust is further kept separate from the other for avoiding the formation of undesirable reaction products. In the scrubb- ing steps, the ammonia and the sulfur trioxide are scrubbed from the exhaust gases within the mist eliminator as previously described.

WHAT WE CLAIM IS: 1. An apparatus for treating resinous articles with various gases, -comprising: means having multiple platforms for loading resinous articles thereonto, having a rotary manifold for directing gases to said resinous articles at multiple treatment stations while avoiding mixing -of gases which react with each other; means for indexing said multiple platforms sequentially around said rotary manifold from one treatment station to another, one of said treatment stations being for injecting a mixture of sulfur trioxide and dry air from a blending means, and another of said treatment stations being for injecting generally gaseous ammoula from a source thereof; a lower manifold for collecting gases that have been thus injected to said Resinous articles at the said treatment stations; and exhaust means associated with said lower manifold.

2. The apparatus of claim 1, vllerein another of the multiple treatment stations is for injecting air to flush out said resinous articles between said sulfur trioxide treatment station and said ammonia treatment station.

3. The apparatus of claim 1 or 2, wherein each treatment station of said rotary manifold includes an upper elbow bore having one end opening into one conduit communi- cating with each of said multiple platforms and a lower elbow bore having one end opening into another conduit communicat- ing with each of said multiple platforms, each of said upper elhow bores has another

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (1)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   percentages of less than I per cent to greater than 20 per cent can be formed and used.

   The desired concentration mixture is formed volumetrically at constant temperature without sophisticated controls. Basically, liquid sulfur trioxide is metered by stroking a pulse pump a preselected number of times into a closed vessel of known volume and temperature.

   More particularly, in this first stage, a source of compressed air is dried, its pressure is regulated at a preselected pressure, such as 40 pounds per square inch. Greater pressures up to 60 or 70 pounds per square inch may be developed. The pressurized air is heated to a desired temperature, usually about 250cm., although temperatures as high as 300 or 350 F. are possible at the greater pressures.

   That heated, pressurized air then flows into a tank of known volume to provide a known quantity of dry air. Into this quantity of dried air is sprayed a preselected volume of sulfur trioxide, the amount being regulated by positively displacing known volumes of the liquid sulfur trioxide and keeping track of the number of such displacements whereby the volume pumped and sprayed into the tank can be accurately determined. The formation of the desired mixture is enhanced by tangentially introducing the heated dry air to maximize the ability of the dry air to quickly heat the sprayed sulfur trioxide to the desired temperature for developing the desired treatment concentration.

   In the next stage, the resinous items to be treated with the sulfur trioxide-air mixture are loaded onto a treatment means which indexes the items in a rotary fashion whereby each item at each particular indexing station of the treatment means is being subjected to a treatment step for which that station is designed. An item to be treated is first loaded onto a loading station. Then it is automati cally indexed by the indexing means to the next station at which time the operator will place another untreated item onto the loading station. This indexing continues from station to station while the items are treated as needed until each item makes a complete revolution back to the loading station at which time it will be removed.

   In the preferred or exemplified method, a total of nine indexing steps rotate each resinous item through nine stations, as follows: The first step is one of flushing the item by injecting dry air. Then, at the second station. the sulfur trioxide-dry air mixture prepared in the first stage of this method is fed to the item. In the third, fourth and fifth stations. no additional gases are introduced, these stations being ones at which the sulfur trioxide proceeds to advantageously treat the item to improve its impermeability to organic chemicals. Excess gases are free to exhaust from the items at the second through fifth stations. The sulfur trioxide-gas mixture remaining is withdrawn at the sixth station where a second flushing step with dry air is effected. This is followed by treating the item with ammonia gas at the seventh station in order to properly neutralize the item that remains slightly acidified by residual sulfur trioxide. The ammonia gas is free to exhaust from the items at the seventh and eighth stations. At the eighth station the item is flushed with air in order to complete the removal of any residual ammonia gas before the item is removed at the ninth station, the loading station.

   The exhaust gases from the second through sixth stations, which-include-sulfur trioxide, are kept separate from the exhaust gases from the seventh t-hrough eighth stations, which include ammonia gas. Each separate exhaust is further kept separate from the other for avoiding the formation of undesirable reaction products. In the scrubb- ing steps, the ammonia and the sulfur trioxide are scrubbed from the exhaust gases within the mist eliminator as previously described.

   WHAT WE CLAIM IS:

   1. An apparatus for treating resinous articles with various gases, -comprising: means having multiple platforms for loading resinous articles thereonto, having a rotary manifold for directing gases to said resinous articles at multiple treatment stations while avoiding mixing -of gases which react with each other; means for indexing said multiple platforms sequentially around said rotary manifold from one treatment station to another, one of said treatment stations being for injecting a mixture of sulfur trioxide and dry air from a blending means, and another of said treatment stations being for injecting generally gaseous ammoula from a source thereof; a lower manifold for collecting gases that have been thus injected to said Resinous articles at the said treatment stations; and exhaust means associated with said lower manifold.

   2. The apparatus of claim 1, vllerein another of the multiple treatment stations is for injecting air to flush out said resinous articles between said sulfur trioxide treatment station and said ammonia treatment station.

   3. The apparatus of claim 1 or 2, wherein each treatment station of said rotary manifold includes an upper elbow bore having one end opening into one conduit communi- cating with each of said multiple platforms and a lower elbow bore having one end opening into another conduit communicat- ing with each of said multiple platforms, each of said upper elhow bores has another

   end for gas-passilig alignment with a pipe in communication with said sulfur trioxide and dry air blending means and with another pipe in communication with a source of dry air, and each of said lower elbow bores has another end for gas-passing alignment with a bore in communication with said ammonia source and with another bore in communication with a source of air.

   4. The apparatus of any one of claims 1--3, wherein said lower manifold has two gates forming two compartments thereof one associated with the station at which sulfur trioxide is injected and one with the station at which ammonia is injected, an exhaust line from one of said compartments and another exhaust line from the other of said compartments.

   5. The apparatus of any one of claims 1 4, wherein said blending means includes a blending tank of known volume, an inlet line from a storage tank of liquid sulfur trioxide to an atomizer within said blending tank. said inlet line having a volumetric metering means; a source of dry air at a predetermined pressure and temperature, an injector communicating with said source of dry air and opening into said blending tank.

   6. The apparatus of claim 5, wherein said blending tank is generally cylindrical, said atomizer is located generally along its axis, said dry air injector directs the dry air generally tangentially within said cylindrical blending tank, and said blending tank includes temperature and pressure controls.

   7. A method for treating resinous articles with various gases, comprising: loading a resinous article onto a platform of a rotary indexing multiple station treatment means; indexing said treatment means from treatment station to treatment station at which respective treatments occur; injecting to said resinous article a mixture of sulfur trioxide and dry air through a path from a blending means: exhausting the mixture or a substantial part thereof from the resinous article: injecting gaseous ammonia to said resinous article through a path different from said path of the sulfur trioxide blend: exhausting the ammonia and any remain in sulfur trioxide blend from said resinous article: and unloading said resinous article from said r otilrs indexing multiple station treatment means 8 The method of claim 7, further comprising injecting dry air to said resinous article between said injecting of the sulfur noxide blend and said injecting of the gaseous ammonia (). The method of claim 7 or 8. further comprising automatically aligning an appropnate conduit means to said resinous article as each of said multiple platforms is indexed from treatment station to treatment station in order to effect the appropriate injecting step at each treatment station.

   10. The method of any one of claims 79, wherein said exhausting step further comprises hydrolyzing and neutralizing said sulfur trioxide blend and said gaseous ammonia after exhaustion from the article.

   11. The method of any one of claims 7-10, further comprising, at said blending means, atomizing liquid sulfur trioxide into a tank of known volume, and injecting dry air at a predetermined pressure and temperature into said tank.

   12. The method of claim 11, wherein said preselected temperature is between 250' to 350 F. and said predetermined pressure is approximately 40 pounds per square inch.

   13. The method of claim 11 or claim 12, which includes injecting dry, heated and pressurized air into said tank as a generally tangential injection.

   14. The method of any one of claims 7-13, wherein said indexing step is carried out nine times.

   15. Methods for the surface sulfonation of resinous articles substantially as herein described with reference to the accompanying drawings.

   16. Apparatus for the surface sulfonation of resinous articles substantially as herein described with reference to and as illustrated in the accompanying drawings.