A Troubled Process for Producing Surfactant Requires Considerable Change

Readers help sort out a sulfonation in shambles.

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THIS MONTH'S PUZZLER
We make an anionic surfactant by reacting oleum (SO3 in H2SO4) with alkyl benzene (C12H25C6H5) in a continuous stirred-tank reactor (CSTR); see Figure 1. The product from our spray dryer is 85% pure, with the remainder being sodium sulfate and water. Ever since we started up this process a year ago, we've had problems: 1) a residue in the product layer in our separator; 2) a heavy black residue in the spent acid at the bottom of the separator — the company that regenerates our H2SO4 has threatened not to take our waste if we don't clean it up; 3) our titration analyzers downstream of the reactor and digester sometimes have fouled tubing — a sample pump failed a few weeks ago because a suction strainer plugged; and 4) startup and shutdown are rough — we can't turn down the capacity of the sulfonator cooler effectively and the smaller jacket control valve can't handle the mid-range cooling requirements. We see a lot of what appears to be burnt product during these periods. Recently, our Coriolis meter, which measures alkyl benzene, corroded out. What can we do to address these problems?


ADJUST THE OLEUM RATE
The problem likely arises from the oleum feed rate being too high relative to the alkyl benzene feed rate causing charring of the alkyl benzene. Very tight molar ratio control and temperature control are necessary to minimize the charring — the blackish material seen in the spent sulfuric acid. Slowing down the oleum feed rate and increasing the residence time in the CSTRs is a potential solution. Additionally, make sure the oleum and alkyl benzene feed control systems are accurately measuring mass flow rates.
Wyatt Winkenwerder, senior research engineer
 Akzo Nobel, Brewster, N.Y.

REVAMP THE PROCESS
Alkyl benzene sulfonation is an exothermic reaction. If the exotherm and stoichiometry are not controlled, the reaction will produce undesirable products that will create the described problems. Process stoichiometry, operating parameters and the chemistry must be precisely controlled. Sufficient residence time must be provided to ensure the desired conversion. Also, I would use a pump for oleum. Relative flow control is important (see Figure 2); many options are available. The processor should select the one that would prevent back flow suggested by corrosion of the Coriolis meter.

Because this is a continuous process, I strongly recommend using a gravity-based separator that will separate two layers and eliminate the use of two pumps: refer to McCabe and Smith's "Unit Operations of Chemical Engineering," McGraw-Hill, 2nd ed., pp. 40–41. The current organic/aqueous separation is fighting two opposing controllers that complicate processing. The addition of water may be necessary to change the densities and facilitate the separation. The existing system can be reconfigured to create a simpler process that will eliminate black residue that is formed due to over-sulfonation of alkyl benzenes.
Girish Malhotra, president
EPCOT International, Pepper Pike, Ohio

CHECK FOR CONTAMINATION
Maybe it's in the water or the materials of construction, i.e., piping, tubing or valves.
Frank Fox Jr., retired,
Houston, Texas


TAKE FOUR STEPS
I suggest the following actions:
1. Aerate the separator/settler sump to remove more of the product.
2. Increase the brine concentration to provide more cooling to the sulfonator, to avoid the over-heating that causes formation of black reside.
3. Replace the Coriolis meter with one using sulfuric-acid-resistant tubing.
4. Install an automatic flushing system for the titration analyzer loop. This will prevent suction strainer plugging.
Donald Phillips, manager
Phillips Engineering, Melbourne, Fla.

TACKLE THREE ISSUES
There are three distinct problems, in order of importance: 1) poor process control; 2) poor separation before neutralization, and 3) backflow from more resistant pipe to less resistant pipe (Figure 3).

Process control must operate effectively during all phases of plant operation. Too often, controls run only smoothly near the nominal capacity. The smaller jacket temperature control valve (TV) can't provide sufficient cooling during either startup or shutdown. The larger reactor chiller TV provides too much cooling during these periods. The obvious solution is a larger jacket TV and increased velocity through the reactor jacket, assuming the pressure drop is not a problem — I've used an inline booster pump to make up for added pressure-drop. Another problem with the reactor heat transfer is the agitation. Seldom is a single impeller enough for good mixing, let alone good heat transfer. More impellers are needed — this may require a new agitator. One way to reduce the load on the jacket TV would be to add a cooled-jacket static mixer; the reactor then becomes a second digester. This may not be enough.

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  • I see two major problems right off the bat if the FD presented is truly reflective of the alkyl benzene (AB) sulfonation process.

    First, the oleum and AB feeds must be added individually to the bulk reactor content, preferably into a high flow circulating loop. AB sulfonations are typically conducted in loop reactors. The inline premixing of oleum and AB will definitely aggravate color regardless of flow ratios.

    Second, I see no water addition to the separator which is needed to reduce the H2SO4 content to the required 70 - 80% by weight for improved settling/separation of the layers. Without the water dilution, the loss of sulfonic acids to the spent H2SO4 will greatly increase color bodies (black residue) removal of which is required by the acid regenerator.

    I suggest seeking assistance with industry specialist.

    Reply

  • H2SO4+CuO->H2O+CuSO4 Are you using copper Tubing? If the reaction energy exceeds the activation Energy for cupric sulfate formation consider lining The tubing near the reactor.

    Reply

  • Hi Tom,

    RE: water addition to separators As the author of the puzzle I should point out that I often leave things out to allow the readers to catch a problem. I am well aware that water is required for the separator. Good catch.

    Reply

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