GB2127834A - A continuous process for making solid, free-flowing water dispersible pva-aldehyde reaction product - Google Patents

Abstract

A polyvinyl alcohol-aldehyde reaction product is produced continuously in a rotating contactor by contacting the polyvinyl alcohol with the aldehyde in an acidic aqueous salt solution. The product can be dried and then sieved to remove oversize particles. A preferred aldehyde is formaldehyde which reacts with the polyvinyl alcohol to produce a reaction product that can be used as a fluid loss control agent in oil fields.

Description

SPECIFICATION A continuous process for making solid, freeflowing water dispersible PVA-aldehyde reaction product This invention relates to a continuous process to make a polyvinyl alcohol-formaldehyde reaction product.

A reaction product of polyvinyl alcohol (PVA) and an aldehyde such as formaldehyde has been found to be an effective water loss control agent to be used in oil fields. See, for example, "New Mud System Gets Field Trial" by J. Block in the Oil and Gas Journal, Jan. 11, 1 982, pg. 79-82; U.K.

Patent Application 2,074,636A where the reaction product is combined with a solid, particulate silicate or aluminosilicate material to form a fluid loss control system; and U.K. Patent Application 2,073,228A where the reaction product is combined with a hydroxy containing aluminum component. The reaction product has been made in batches in the laboratory by reacting polyvinyl alcohol with sub stoichiometric amounts of an aldehyde such as formaldehyde in a 16% sodium sulfate solution. The pH of the sodium sulfate is adjusted to about 2.3. The PVA is then slurried with this pH adjusted 16% sodium sulfate solution and then formaldehyde is added in the form of formalin which is a 37% aqueous solution stabilized with methanol. The mixture is heated to about 16-21 0F (60-700C) for about 10-15 minutes.The reacted solid is filtered to remove excess solution. The resultant filter cake is then placed in a batch dryer where it is dried to its prerequisite total volatile content which is approximately 3 wt.% (determined at 1000C). The solid particles are ground and screened to give the desired size fraction which is packaged. Using this batch reactor and the required batch dryer results in large clumps or agglomerates. These large particles have a "gummy" appearance and they stick together. As a result these large particles must be ground to obtain the smaller particle sizes preferred for packaging.

In addition to the deficiency that this is only a batch process, it also requires five unit operations involving a reactor, a centrifuge to separate the product from the reactor liquid, a dryer, a grinder to reduce the size of the particles produced and a sieve to ensure obtaining the required on size particles for packaging.

The present invention provides a continuous process for producing a polyvinyl alcohol-aldehyde reaction product. This process reduces the number of unit operations required to produce the polyvinyl alcohol-aldehyde reaction product, and makes it unnecessary to centrifuge the product from the reactor liquid or to grind a large amount of oversize particles from the dryer. The polyvinyl alcohol-aldehyde reaction product made by the new process can be small enough size moist particles that can be taken directly from the dryer and packaged for use.

This new process comprises (a) adding to a rotating continuous reactor to form a mixture i) polyvinyl alcohol, ii) an aldehyde, and iii) an aqueous salt solution adjusted to have an acidic pH; (b) mixing the mixture of step (a) in the reactor until a polyvinyl alcohol-aldehyde reaction product is obtained; and (c) drying the polyvinyl alcoholaldehyde material.

The process of the invention for the continuous production of a polyvinyl alcohol-aldehyde reaction product may comprise simultaneously feeding to a rotating continuous contactor solid polyvinyl alcohol, an aldehyde and a warm salt solution such as a preferred 16% sodium sulfate solution that has been adjusted to a pH in the range of about 1.5 to 3.0, more preferably from about 1.9 to 2.3, and heated to about 900F (320C). In the preferred embodiment the aldehyde is formaldehyde which is supplied in the form of 37% formaldehyde in water solution stabilized with 10% methanol. The resultant mixture is contacted for a relatively short period of time, which can be less than one minute and, more preferably, in the apparatus described hereafter for approximately 35 seconds, before being continuously discharged to a continuous dryer.

The moist reaction product passes through the vented dryer which operates under atmospheric pressure at a relatively low temperature of approximately 1 400F (600 C). After a residence time of about 140 minutes a dry, free flowing material having a total volatility, T.V., of between 3 and 4 wt.% is produced as measured by an Ohaus Moisture Determination Balance. This desired dried, uncaked finished product is discharged directly to a packaging operation.

A comparison of the batch operation and this continuous process shows that the batch operation requires 5 unit operations involving a reactor, a centrifuge to separate the product from the reactor liquid, a dryer, a grinder to reduce the size of the large particles produced by the batch process and a sieve to insure obtaining the required on size particles for packaging. The continuous operation according to this invention requires only 3 unit operations involving the reactor, the dryer and the sieve to remove any oversize particles so that only the proper, smaller size particles are packaged.

The moist product leaving the continuous reactor can also be dried by a batch drying process where the material is dried in an oven.

The single Figure of the accompanying drawings is a block diagram illustrating the process of this invention.

When using an alumina viscosifier, it is desirable to have a compatible water loss control agent so that the system has a total fluid loss of less than 10 cc. when measured by the API procedure RP-13B described infra. One example of a compatible water loss agent is a dispersible polyvinyl alcohol-aldehyde reaction product.

This reaction product has previously been made in batches and by the present procedure it can be made continuously and with less process equipment.

In conducting the continuous process, solid particles of polyvinyl alcohol are added to the inlet of the rotating continuous reactor. A preferred form of PVA is Gelvatol 20-90 made by Monsanto Industrial Chemicals Co. The molecular weight for the Gelvatol family PVA can vary from about 2,000 to 125,000 with the Gelvatol 20-90 having a molecular weight of 125,000. There are many manufacturers of PVA. The preferred PVA weight average molecular weight is at least 20,000 with a more preferred range being from about 90,000 to 200,000. In the preferred forms the PVA is at least about 75 percent hydrolyzed and more preferably from about 80 to 95 percent hydrolyzed.

After entry of the solid PVA particles in the mixer reactor they are contacted with a salt solution and an aldehyde preferably in a solution form. In the more preferred embodiment illustrated in the Figure, the aldehyde solution, which is preferably formaldehyde, is injected into a sodium sulfate solution so the two materials have an opportunity to thoroughly mix before the liquid mixture is fed to the solid PVA particles in the reactor.

The concentration, acidity and temperature of the sodium sulfate solution are controlled for optimum use. The optimum sodium sulfate concentration is about a 1 6 weight % solution because this is approaching a saturated solution and any higher amount would begin to salt out.

Lower concentrations could be employed, but that would add additional water to the final reaction product which must later be removed by the dryer.

The pH of the sodium sulfate solution is also controlled. In order for an aldehyde to react with PVA it is necessary to have acidic conditions. The preferred pH range when using formaldehyde as the aldehyde is from about 1.5 to about 3.0. For this formaldehyde system at lower pHs such as 1.4 the resulting reaction product does not have the desired controlled fluid loss property when evaluated under the high temperature fluid loss test. Similarly if the pH is too high such as around 2.8, the materials do not react and thus the resulting reaction product does not have the desired cross-linked properties.

The PVA-aldehyde reaction proceeds more satisfactorily at elevated temperatures. However, if external heat is applied to the rotating reactor, undesirable reaction deposits develop on the inside of the reactor. An optimum way to supply heat to the reactor is to preheat the sodium sulfate solution which is the largest liquid component added to the reactor. For the apparatus described in Example 1, good results are achieved when the solution is heated to about 900F (320C). For this formaldehyde system, heating to only 700F (21 OC) did not work as well. On the other hand, if the solution is heated too high, then the product becomes tacky and difficult to handle. A preferred temperature range to preheat the solution is from about 850F to 1400F (29-600C).

Up to this point, only the preferred sodium sulfate solution has been discussed. The purpose of this solution is to prevent the PVA from solubilizing in the acid solution. When the PVA is commercially produced, the PVA is recovered from the reaction solution by adding a salt such as sodium sulfate that causes the dissolved PVA to form an insoluble solid. Here a similar procedure is being used; by adding the salt the PVA is prevented from dissolving back into solution.

Sodium sulfate is the preferred salt because it is very efficient in preventing the PVA from dissolving while it keeps the PVA swollen for reaction. It is also compatible since it is the salt used commercially when making PVA. However, other salts could be used such as sodium chloride, sodium phosphate, sodium carbonate, potassium chloride, potassium sulfate, etc.

The reaction product is made by using an aldehyde which reacts with the PVA. The preferred aldehyde is formaldehyde and the preferred form is the commercially available formalin which is an aqueous solution of 37% formaldehyde which has been stabilized with from 6-1 5% methanol. Suppliers of this material include J. T. Baker Chemical Co., Hercules, and Ashland Chemical Co. Other commercial grades of formaldehyde and its polymers could be used.

Such commercial grades include 44,45 and 50% low-methanol formaldehyde, solutions of formaldehyde in methyl, propyl, n-butyl, and isobutyl alcohol, paraformaldehyde and trioxane.

When using solid paraformaldehyde, care must be taken that it all dissolves. If it has not dissolved, then the solid material may remain unreacted when the reaction product is formed and this paraformaldehyde can produce unwanted hazardous vapor when it and the reaction product are subsequently heated in the dryer.

Other aldehyde containing or generating reactants are organic chemical compounds which contain at least one aldehyde group therein as are well known and include, for example, formaldehyde, acetaldehyde, proprionaldehyde, glycoaldehyde, glyoxylic acid and the like or polyaldehydes i.e., organic compounds having more than one aldehyde group in the compound, such as glyoxal, paraformaldehyde and the like.

Other suitable aldehyde reactants include aldehyde generating agents i.e. known organic compounds capable of forming an aldehyde group in situ, such as melamine-formaldehyde monomeric products and derivatives such as tri and hexa(methylol) melamine and the tri and hexa (C1-C3 alkoxymethyl) melamine. Such materials can be formed by known conventional methods.

The alkyl blocked derivatives are commercially available, are stable to self polymerization and are, therefore, preferred. Of all of the aldehyde reactants, the preferred reactants are paraformaldehyde and formaldehyde.

The amount of formaldehyde added to the reaction mixture must be controlled. If too much formaldehyde is added the product is over crosslinked yielding a material that does not have the desired low controlled flow loss value of less than 10 cc.

When the aldehyde reacts with the polyvinyl alcohol, two OH groups react with one aldehyde group. Based on this stoichiometry the amount of aldehyde added is at least about 0.1% and preferably from about 1 to 80 and most preferably from about 2 to 50 percent of stoichiometry of an aldehyde reactant based on the hydroxyl content of the polyvinyl alcohol. On a weight basis, the preferred weight ratio of formaldehyde to polyvinyl alcohol is about 0.0095:1. Excess aldehyde can be used. The particular amount of aldehyde agent will depend on its solubility in the aqueous reaction media, and its reactivity as is known and determinable by conventional means.

As indicated above, the preferred technique to add the aldehyde and the sodium sulfate solution to the mixer reactor is to first add the aldehyde to the sodium sulfate solution. As seen in the Figure, the heated sodium sulfate solution is fed into an enlarged pipe where an injection tube is inserted to feed the aldehyde solution. These two liquids mix and then proceed to flow into the mixer reactor.

As the solid PVA particles travel through the reactor, they mix-and react with the sodium sulfate and aldehyde solution to form the desired reaction product. Using a contactor such as the Zig-Zag Blender in Example 1, it is possible to have a contact time which is less than one minute and which, for this specific reactor, is on the order of only about 35 seconds. The resulting reaction product is preferably immediately dried to prevent any further reaction.

The type of drying operation is not critical and can be done either with -a batch dryer or a continuous dryer. Since the reactor is continuous, the preferred embodiment is to also use a continuous dryer which is vented to the atmosphere. Because of the relatively low water content, it is possible to use a low temperature dryer which operates at a.temperature of 1 400 F (600 C). This lower temperature is desired to prevent any thermal cross-linking of the reaction product which would result in a brownish colored material. Further benefits of using this lower temperature is that energy is conserved. Using this dryer and a residence time of between 2 and 3 hours, it is possible to produce a dry, free flowing product which has a total volatility of only 3 to 4 weight %. These particles are generally of the desired small size so that they can be directly packaged.A sieve screen such as a 6 mesh screen (aperture 3.36 mm) can be used to remove any of the oversize particles before packaging.

Test Procedures The fluid loss property of this reaction product is determined by the American Petroleum Institute procedure API No. RP-13B. At ambient temperature a sample is placed in a vessel having a screen on the bottom over which a filter paper is placed. Pressure (100 psig; 690 kPa) is applied and the amount of liquid that flows out in 30 minutes is measured and identified as the control total fluid loss, TFL. It is desirable to have the TFL value less than 1 5 cc. and more preferably at a value of 10 cc. or less.

An additional test for fluid loss is the roller oven test where the reaction product is heated on a rolling device in an oven at 2500F (121 0C) for 1 6 hours. This is intended to simulate the conditions in a well where shear forces exist in addition to elevated temperatures. The TFL is determined on the cooled sample and again it is desirable to have a TFL value less than 1 5 cc. and preferably at a value of 10 cc. or less.

In both of these tests the test liquid contained 2.4% AIO(OH) as described in U.S. Patent No.

4,240,91 5, the content of which is incorporated herein by reference and 1.696 of the poly(vinyl alcohol)-aldehyde product.

Having described the basic aspects of our invention, the following examples are given to illustrate specific embodiments thereof.

EXAMPLE 1 In this example, the primary reacting or contacting equipment is a Patterson-Kelly Zig-Zag Blender Model 8-CLSS made of 316 Stainless Steel. It has a tube diameter of 9 inches (23 cm), a working length of 31 inches (79 cm) and it operates at 32 revolutions per minute. To this contactor, polyvinyl alcohol, Gelvatol 20-90 made by Monsanto Industrial Chemicals Co., was fed at a ratio of 2.5 Ibs (1.13 kg) per minute.

Concurrently, a 16% sodium sulfate solution adjusted to a pH of 1.65 by adding sulfuric acid and warmed to a temperature of 900F (320C) was added. This liquid was injected through a (centrifugal) intensifier (droplet producing) system at a feed rate of 2.0 Ibs (0.9 kg) per minute. A formaldehyde solution (37% formaldehyde in water containing 10% methanol) was co-injected at a ratio of 1.2 my/50 g of PVA along with the 16% sodium sulfate solution into the dispersed solid PVA. The process was run continuously for a period of two hours. The material had a short residence time in the reactor and it then passed to a Torus Disc Dryer made by Strong and Scott Mfg.

Co. operating at a temperature of 1 400F (600C).

In the dryer the residence time was about 2 hours.

Using the test-procedures described earlier, the resulting product had the following properties.

Fluid Loss Test Results Control TFL 9.3 cc Roller Oven TFL 7.1 cc These properties ofthis continuously produced material were about equal to or better than the product produced in the batch reactor to be described below. All materials produced by this contacting method have been adjudged excellent in terms of water loss control properties.

COMPARISON EXAMPLE 1 This comparative example describes a batch process for making the reaction product.

In a 200 gallon (750 litre), glass lined jacketed reactor 76 gallons (288 litres) of a 16% NaSO4 solution was added. This solution has been adjusted to a pH = 2.8 + 0.2 with H2SO4. The reactor agitator was started (70 RPM) and 250 pounds (113 kg) of Gelvatol 20-90 added.

The mixture was stirred for 1 5 minutes and then 34 pounds (15.4 kg) of solid paraformaldehyde were added. The reactor was heated to 1400F (600 C) and maintained at that temperature for 30 minutes. The reactor was then cooled to 1000F (380C) and approximately 1/3 of the batch was allowed to discharge into a cloth lined basket centrifuge. The solids were separated from the mother liquor as centrifuging continued for 10 minutes. The centrifuge was unloaded manually and the material placed directly into drying trays. This loading, centrifuging, unloading operation was repeated two more times to complete the discharge of the reactor.After all of the material was placed into drying trays, the trays were loaded into a batch tray drier which was operating under vacuum (28 inches, 71 cm, of mercury) and at a temperature of 1 850F (850C).

Drying continued for about 1 6 hours until the total volatility was between 35% as measured on an Ohaus Moisture Determination Balance.

The dryer was then discharged and the content ofthe trays was cut into 4" x 4" (10 x 10cm) pieces. These pieces were ground in a mill and sieved through a 6 mesh screen (aperture 3.36 mm) to remove oversized materials. The oversized materials were reground and sieved.

Approximately 240 Ibs (109 kg) of on-size material was obtained through this process which was then packaged.

Using the same test procedures, the product had the following properties.

Fluid Loss Test Results Control TFL 7.1 cc Roller Oven TFL 13.6 cc The batch process required 5 units operations (reactor, centrifuge, dryer, mill and sieve) and 12 man-hours to make the 240 pounds (109 kg). In contrast, the continuous operation only required 3 unit operations (reactor, dryer, and sieve) and only about 96 operator minutes to make the same quantity of product.

EXAMPLE 2 This example illustrates another procedure to continuously produce the reaction product and to have batch drying.

The procedure of Example 1 was followed to continuously make the reaction product. The product was placed in a Pyrex glass tray and placed in an oven at 1 400F (600C) overnight to dry. The resulting produce had the following properties.

Fluid Loss Test Results Control TFL 9.2 cc Roller Oven TFL 8.0 cc EXAMPLE 3 This example illustrates another polyvinyl alcohol used in the continuous process.

The continuous procedure of Example 1 was followed except that the polyvinyl alcohol was 540S made by Air Products Company and the pH was 1.9 instead of 2.3. The resulting product had the following properties.

Fluid Loss Test Results Control TFL 5.9 cc Roller Oven TFL 5.2 cc

Claims (15)

1. A process for the continuous production of a polyvinyl alcohol-aldehyde reaction product comprising (a) adding to a rotating continuous reactor to form a mixture i) polyvinyl alcohol, ii) an aldehyde, and iii) an aqueous salt solution adjusted to have an acidic pH; (b) mixing the mixture of step (a) in the reactor until a polyvinyl alcohol-aldehyde reaction product is obtained; and (c) drying the polyvinyl alcohol-aldehyde material.

2. A process according to claim 1, wherein the aldehyde is formaldehyde.

3. A process according to claim 2, wherein the weight ratio of formaldehyde to polyvinyl alcohol is about 0.0095:1.

4. A process according to claim 2 or 3, wherein the formaldehyde is in the form of an aqueous solution of formaldehyde stabilized with methanol.

5. A process according to claim 4, wherein the formaldehyde concentration is about 37% by weight.

6. A process according to claim 2, wherein the formaldehyde is added as paraformaldehyde and the amount added is less than the stoichiometric amount needed to react with the polyvinyl alcohol.

7. A process according to any of claims 1 to 6, wherein the pH of the salt solution is from about 1.5 to about 3.0.

8. A process according to claim 7, wherein the pH is from about 1.9 to 2.3.

9. A process according to any of claims 1 to 7, wherein the salt solution is a sodium sulfate solution.

1 0. The process according to claim 9, wherein the sodium sulfate concentration is about 1 6 weight percent in the aqueous solution.

11. A process according to claim 9 or 10, wherein the sodium sulfate solution and aldehyde are first premixed before being mixed with the polyvinyl alcohol.

12. A process according to any of claims 1 to 11, wherein the salt solution is heated to a temperature between about 850F and 1400F (29 to 600 C).

13. A process according to any of claims 1 to 12, wherein the polyvinyl alcohol has a weight average molecular weight of at least 20,000.

14. A process according to any of claims 1 to 12, wherein the polyvinyl alcohol has a weight average molecular weight of from about 90,000 to 200,000 and is at least about 75 percent hydrolized.

15. A process according to claim 14, wherein the polyvinyl alcohol is from about 80 to 95 percent hydrolyzed.

1 6. A process according to any of claims 1 to 15, wherein the drying is done in a continuous dryer.

1 7. A process according to any of claims 1 to 15, wherein the drying is done in a batch dryer.

1 8. A process according to claim 1 substantially as described in Example 1,2 or 3.

1 9. A polyvinyl alcohol-aldehyde reaction product produced by the process of any of claims 1 to 18.