Lab scale contact process for H2SO4 (report)

(I realize this has been discussed before, but not recently AFAIK, so I hope I'm not breaking any rules)

I would like to report success at the contact process for sulfuric acid.
In (some of?) the EU, sulfuric acid above 50 % concentration has been banned as part of an anti-terrorism package. While it is possible to buy such (50%) acid, and concentrate it by boiling it down, it is difficult to achieve very highly concentrated acid since decomposition/evaporation losses get more significant the higher the acid concentration becomes. Therefore, it would be practical to be able to fortify existing acid up to (or beyond) 100 %. To achieve this I have experimented with a lab scale adaptation of the contact process. For this stage of the experiments, I decided to avoid the additional complication of a sulfur burner and instead generate the SO2 from a wet process.

SO2 from the reaction of sodium metabisulfite with hydrochloric acid was mixed with air from an aquarium pump and dried in a silica gel column (fig 1). Indicating silica gel is very practical here, since you can easily see when it is time to refresh it.

See attached image 1: Production and drying of SO2

The dry gas stream was fed into a quartz tube furnace containing catalyst on silica gel (kitty litter).

See attached image 2: Furnace inlet

The catalyst was prepared by dissolving vanadium pentoxide in oxalic acid, forming a clear blue solution. This solution was then absorbed in (and adsorbed on) kitty litter silica gel, and dried. Afterwards, it was heated to ca. 200 C to decompose the oxalate and leave V2O5. A few centimeters of this catalyst were placed into the furnace and held in place with ceramic wool (aluminum silicate). The furnace was heated to ca. 450 C by means of a nichrome element and an SCR. I had no active temperature control.


The stoppers for the furnace are made of PTFE which I turned on my lathe. A tight seal was ensured with PTFE plumbers tape.
From the furnace, the gas stream was led into an absorption tower consisting of two straight line vacuum adaptors and a Graham condenser

See attached image 3: Absorber column

I would have liked my absorber to be a packed column, but this was all I had access to at the time.
Concentrated sulfuric acid (144.4 g, of nominally 96%) was run through the tower from the pressure equalizing dropping funnel at a low enough rate that it formed a stream at the “bottom” of the windings of the coil without blocking gas flow. This corresponded to about one drop per second. When all of the sulfuric acid had run through, the bottom 250 ml RBF was removed, stoppered and weighed to monitor weight gain.

Results
The RBF including acid, stopper and cork ring was weighed before the first run, and after each run thereafter:

Run 1: 15.8 g metabisulfite, 7.4 g mass gain, 55.6% SO3 yield
Run 2: 62.1 g metabisulfite, 28.9 g mass gain, 55.3% SO3 yield
Run 3: 37.3 g metabisulfite, 22.1 g mass gain, 70.4% SO3 yield

“Metabisulfite” notes how much of this reagent the SO2 generator contained at the beginning of the run. A slight excess of aqueous hydrochloric acid was added through the dropping funnel mounted on the three-necked flask. The last neck was fitted with a thermometer adaptor for the tube from the aquarium pump. This way, the liberated SO2 was admixed with the entering air and carried through the system.
The yield calculation is based on each metabisulfite ion liberating 2 molecules of SO2, and is the overall, effective yield, assuming that all mass gain is due to SO3 absorption.
The hoses I used were PVC from the generator to the furnace, PTFE from the furnace to the absorber (except for a small piece to connect the PTFE to the glass vacuum adaptor), and PVC again from the top of the absorber to the exhaust bubbler. Note that where SO3 had come in contact with anything other than glass or PTFE, extensive charring was the result. The charring of the PVC hose before the furnace was due to an experimental run with pure oxygen (from electrolysis) as the carrier gas. In this run, the flow rate was too low, and quite a bit of back flow occurred. Likewise, the charring after the absorber was primarily due to another experiment with a simple gas washing bottle for absorbing the SO3 into the concentrated sulfuric acid. Doing it this way is completely ineffective, and practically all of the product was lost as acid mist in the exhaust bubbler.
The exhaust bubbler itself is there primarily as a means to monitor the process. Flow rate can be judged by the bubbles, while absorption efficiency can be seen from how much acid mist is produced.
When the process is begun, but the flow of sulfuric acid has not yet been turned on, an impressively thick, white fume, much like stage smoke (dry ice in water), is produced at the exhaust bubbler.








Analysis
The product was observed to be fuming, much like highly concentrated nitric acid.

A small amount was transferred to a small pre-weighed flask and weighed precisely (1.660 g). It was then slowly diluted with demineralized water (to ca. 20 ml) and titrated with dilute NaOH solution which had been calibrated with analytical potassium hydrogen phthalate as primary standard.
The sample titrated as 102.2 % sulfuric acid, corresponding to 9.9 % free SO3.




[Edited on 6-2-2017 by Microtek]

[Edited on 6-2-2017 by Microtek]

Nice work!

Indicating silica gel: Is this something you made or is it commercially available?Nvermind, I see it's available at Walmart. . Nice use of otc materials.

[Edited on 6-2-2017 by Magpie]

Quote: Originally posted by DJF90

Edit: Actually, are you sure its V2O5 formed on the support after calcination? I recall oxalic acid can reduce some metal species, particularly those in the higher oxidation states. I suspect the vanadium is not +5 in the solution, given the blue colouration, but whether it returns on activation at temperature or not I don't know? [Edited on 6-2-2017 by DJF90]

First of all: Thanks for the kind words everyone!

@ DJF90:
I tried using ammonium metavanadate at first, but couldn't get the V2O5 to dissolve in aqueous ammonia. I thought, maybe I wasn't using a high enough concentration (I found, by titration, that my ammonia solution had dropped to ca. 21% over the years). However, when I researched preparation procedures of ammonium metavanadate, I discovered that it is actually quite insoluble. I wanted a soluble vanadium salt that could be deposited on a suitable support and then be turned back into V2O5. Vanadyl oxalate was what my research turned up.
It is prepared by an adaptation of the process in US3689515: Three equivalents of oxalic acid dissolved in water is heated to ca. 90 C, and one equivalent of vanadium pentoxide is added with stirring. The solution turns an impressive peacock blue as the reaction proceeds. I then added potassium sulfate to act as a promoter, since I have also read that this is advantageous.
After cooling, I added some of the solution to a spoonful of kitty litter zeolite. I used enough solution that not all of it was absorbed, since I wanted to be certain that the outer surface was coated as well (since I am not certain that much of the reaction will take place on the inside surface). I swirled the beaker intermittently as the excess liquid evaporated to leave the catalyst. After air drying, I heated it in the oven at ca. 200 C, which gave a colour change of the (outer) surface to orange/red.
I figured that, since the catalytic process is probably a cycle of oxidation and reduction, it probably wouldn't be too sensitive as to the exact oxidation state of the vanadium.

Pictured below is a comparison of the different stages of the catalyst preparation:

Sample at the left is untreated kitty litter zeolite. Top mid is after air drying of the vanadyl oxalate impregnated zeolite, and right is after oven drying. Bottom mid is after calcining for about 30 seconds at red heat (blowtorch). Note that the colouring of the final product only develops after standing for a few minutes; immediately following the calcining, it is almost colourless.

Quote: Originally posted by wg48

... silica gel types of kitty litter ... additives ... some may be a clay type ...

The most OTC source of sodium metabisulfite is likely from stump remover. Bonide sells a stump out which is listed as 99% metabisulfite on the sds. Some stump removers are potassium nitrate as well, so check the MSDS. Although both nitrate and metabisulfite are useful. Other than that look on eBay or some other website, plenty of chemicals can be found online.





I got 450g (one pound) for about USD$8 from a local hardware store.

sounds good. i will try to find sodium metabisulfate

@Microtek: to go from sulfur to sulfuric acid, i think you would need vanadium(V) oxide as catalyst.
hope this is easy to find

I realize this thread is more than 3 years old but might be more relevant than ever before.
Last few days I have been reading up on the process while thinking it might be out of reach for backyarders, until I found this conversation.

@Microtek I am curious if you ever followed up on your experiments and if you would be so kind as to draw your reactor.

I am planning to investigate a viable way to use pressure to shift the equilibrium of SO2 + O2 -> SO3
According to the sources I have found this can be shifted with as little as <2 Bar of pressure which even regular glassware might tolerate.
The engineering part is probably the biggest challenge.

This source has a very easy to read summary of the process:
https://www.chemguide.co.uk/physical/equilibria/contact.html


*Edit
To get the juices flowing I drew up a possible reactor, please let me know what you think.
I don't want to hijack this thread , if the mods prefer a new thread please say so and I'll open up a new one.




[Edited on 6-8-2020 by Belowzero]

Found a relativ simple looking Build up allmost Glasware here...
Sulphur trioxide - the sulphuric acid contact process
Its not cheap there but you should be able to re - build this
SO3 and Contact Process

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[Edited on 29-1-2021 by xxxhibition]

Quote: Originally posted by Belowzero

I am planning to investigate a viable way to use pressure to shift the equilibrium of SO2 + O2 -> SO3 According to the sources I have found this can be shifted with as little as <2 Bar of pressure which even regular glassware might tolerate.