JPS6043164B2 - Petroleum emulsion separating agent for separating crude oil emulsions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The ability to separate oil-in-water petroleum emulsions with block polymers from ethylene oxide and/or 1,2-propylene oxide, as described for example in US Pat. No. 2,964,478. is publicly known.

This type of emulsion consists of water in which oil is emulsified in the form of fine droplets. The compounds according to this document are not suitable for emulsions of the opposite configuration, ie water-in-oil emulsions, in which water is emulsified in the form of fine droplets in the oil phase. However, the separation of the latter type of emulsion, i.e. the dehydration of newly mined crude oil, is a very important problem in the petroleum industry, and many attempts to solve it have been proposed in numerous patent specifications and literature. ing. It is also already known to use block polymers of this type as separating agents for water-in-oil emulsions.

For example, according to German Patent Application No. 154,525, dehydration methods are known by adding various alkylene oxide polymers and compounds with hydrophilic end groups derived therefrom to water-in-oil emulsions. However, these do not exhibit their full activity quickly enough, and often only at elevated temperatures, as will be shown later. As is currently known, these compounds, after their use, produce very high contents of residual moisture,
They leave residual salts or residual emulsions and are only fully effective, especially in the case of a few special types of oils. Water-in-oil emulsions are often high in viscosity, as they are obtained by chemical or electrochemical manipulations with low contents of water, salt and possibly residual emulsions required for later processing. Heated at an energy cost.

However, the temperature at which water-in-oil emulsions are mined, i.e. 10~
It is desirable that this emulsion can be separated even at 40° C. without adding an appropriate decomposing agent and heating.

It is not possible to find a universal separating agent for all types of crude oil, as experience shows that the composition of crude oils is different.

Nevertheless, it is desirable to develop separating agents that are compatible with many similar oil types. This is because otherwise a very large number of products would be required for this purpose. German Patent Application No. 2227546
The document describes a rapid dehydration process for crude oil by the addition of substances with a demulsifying action based on derivatives of polyalkylene oxides.

This process involves adding to crude oil at least one polyalkylene polyamine having at least two repeating alkylene imine units in the molecule, oxyalkylated completely on the nitrogen atoms by 10 to 30 units each. It is characterized by German Patent Application No. 24357
No. 13 describes that this type of quaternized polyalkylene polyamine derivatives are also effective.

DE 2013820 describes mixtures of oxyalkylated isoalkylphenol formaldehyde resins and oxyalkylated polyhydric alcohols as petroleum emulsion separating agents. The present inventors unexpectedly discovered that the isoalkylphenol formaldehyde resin described in German Patent No. 20138 and the isoalkylphenol formaldehyde resin described in German Patent Application No. 222
7546 and/or German Patent Application No. 24
It has been found that the combination with the substances described in No. 35713 is particularly effective.

According to the invention, the petroleum emulsion separating agent contains 2
5 to 75% by weight of oxyethylated and/or oxypropylated products of isoalkylphenol formaldehyde resins, each containing oxyalkylate groups having 4 to 5 alkylene oxide units;
8-12 bonded to the p-position to the oxyalkylate group
3-3C with an isoalkyl group having 3 to 3 carbon atoms
(containing a penzole nucleus of) CA) and 75-25% by weight of at least oxyalkylated completely on the nitrogen atoms by 10-200 f8, respectively, having at least 2 repeated alkyleneimine units in the molecule. Based on oxyalkylated compounds containing one polyalkylene polyamine (B) as active ingredient.

Component B may be quaternized on the nitrogen atom. This combination does not simply result in additive properties, but results in petroleum emulsion separating agents with new and improved properties based on synergistic effects.

The new separating agent is particularly suitable for the separation of difficult emulsions and
Particularly clean wastewater is obtained. This separating agent is extremely economical since its consumption is extremely small. The separating agent thus obtained completely separates the emulsion very quickly and is effective even at temperatures just above the pour point of the crude oil. The oxyalkylated alkyl phate formaldehyde resin A has the following formula (wherein X is an integer of 8 to 12, n
is an integer between 2 and 3, y is an integer between 4 and 50, and z is an integer between 3 and 3.
(meaning an integer of 30).

The isoalkylphenols used for the condensation with formaldehyde and the subsequent oxyalkylation are those having 8 to 12 carbon atoms in the isoalkyl group bonded in the p-position to the phenolic hydroxyl group.

Preferably, isooctyl, isononyl or isododecylphenol is used. The condensed and oxyalkylated resin has 3 to 3, preferably 4 to 1, phenolic nuclei and 4 to 50 per phenolic unit.
ff! (mol) is oxyethylated and/or oxypropylated. In particular, oxyethylated isooccluphenol formaldehyde resins having 20 to 30 ethylene oxide units and 4 to 1 phenol nucleus are used. The resins are produced in a known manner by basic catalytic reactions, with the formation of resol-type condensation products.

Novolaks are formed in the presence of acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluolsulfonic acid or boric acid.
The condensates obtained by both methods are equally suitable as starting materials for the preparation of mixture component A. Both condensation methods are carried out at 120-150'C in an inert reaction medium. The reaction medium is an organic solvent having a boiling point of about 15(s) that is chemically inert under the reaction conditions, such as xylol, heavy benzene or tetralin. Solvents that are inert under the reaction conditions may remain in the product after the condensation reaction. This product is then prepared in a manner known per se, for example in a stirred autoclave, in the presence of a basic catalyst at 120 DEG -135 DEG C., preferably at 125 DEG -135 DEG C.
C. and a pressure of 2 to 12 gauge atmospheres, preferably 3 to 8 gauge atmospheres, with ethylene oxide and/or propylene oxide.

The preparation of component A is known from German Patent No. 201382.

Mixture component B is described in DE-A-2227546.

These compounds can be obtained by a one-step or multi-step process.

In the case of a two-step method, the operation is performed as follows, for example.

In the first step, 1 to 5
In a pressure vessel equipped with a stirrer in the presence of 8% water
0 to 100 (!, a sufficient amount of alkylene oxide is reacted to saturate all valences of the nitrogen atom condensed with the hydrogen atom to produce the corresponding aminoalkanol. In the second step, water optionally under reduced pressure, about 0.5 to 2% by weight of an alkaline catalyst, such as sodium methylate, potassium hydroxide, sodium hydroxide, basic ion exchange, to the water-free amino alcohol of the first stage. and the like, followed by further oxyalkylation using the required amount of alkylene oxide at about 125 DEG-135 DEG C. In a one-step process, the reaction can be carried out, for example, as follows.

The total amount of alkylene oxide is injected into the presence of a water-containing or water-free basic catalyst as defined above, and 125
The reaction is terminated at a temperature of ~135°C. Although higher proportions of polyalkylene glycol ethers may then be formed as mentioned above, it is essential that the raw materials for producing the compounds added according to the invention have an essential influence on the desired properties of the product. The substance is ethyleneimine and/or
Alternatively, it is a polyalkylene polyamine obtained from propylene imine by a method known per se. Preference is given to starting from ethyleneimine. Polyalkylene polyamines have at least two repeating alkylene imine units in the molecule. Polyethyleneimines having 10 to 30(1) repeating ethyleneimine units are particularly useful for this invention. In the oxyalkylation, suitable customary alkylene oxides are used, such as ethylene oxide, 1●2-propylene oxide, 1●2- and 2●3-butylene oxide or isobutylene oxide, styrene oxide or cyclohexene oxide, in particular propylene oxide and Examples include ethylene oxide.

Various alkylene oxides alone or together,
It can be reacted with polyalkylene polyamines according to the block copolymerization or copolymerization format.

When operating in two stages, the alkylene oxide can likewise be used alone or in a mixture in the first stage.

In the second step, and in the case of the one-step method, then proceed as described above. It is preferable to use propylene oxide alone or to carry out the reaction in the form of block copolymerization using propylene oxide and ethylene oxide.

In the latter case, in the first stage 1,2-propylene oxide is injected to form the corresponding propanolamine, followed by further propylene oxide and finally ethylene oxide, with a proportion of propylene oxide of up to 1:15. to ethylene oxide gives satisfactory results. However, it is also possible to operate in reverse, ie to press first the ethylene oxide and then the propylene oxide, for example from 20:1 to 1:2.
Preferably, a ratio of ethylene oxide to propylene oxide of 0 is chosen. Both methods can be carried out in one or two stages. When operating in the form of copolymerization, the ratio of propylene oxide to ethylene oxide is 1:
A mixture (gas mixture) of up to 15 propylene oxide and ethylene oxide can be used.

The aforementioned possibilities can in principle also be used for the other aforementioned alkylene oxides, and the ratios can be chosen essentially arbitrarily if the alkylene oxide is not used alone, but when used in combination with ethylene oxide. are press-fitted at the above ratio taking into consideration the molecular weight of each.

However, it is important in all oxyalkylation methods that 10 to 3
0α, preferably 60 to 15 alkylene oxide units are present in the final molecule.

Mixture component B can also be used in quaternized form.

Suitable quaternizing agents are known compounds, such as alkyl halides such as methyl chloride, methyl bromide or ethyl iodide, as well as dimethyl sulfate and similar substances. Since quaternization is a reaction well known to experts, its explanation will be omitted. The separating agent according to the invention can be prepared by simply mixing the active substances or by dissolving them in the solvents mentioned below. In that case, component A is 25 to 75% by weight, preferably 40% by weight.
Up to 6% by weight, component B can be added from 75 to 25% by weight, preferably from 60 to 4% by weight. The separating agent is preferably used as a solution due to its better quantification properties.

As the solvent, only a mixture of an organic solvent (for example, methanol) and water or an organic solvent having a boiling range of 50 to 200 C is used. Typical examples include toluol, xylols, tetrahydrofuran, dioxane, lower alcohols, These include light benzene fractions in the boiling range mentioned above. Preferably, when a solution is used, the active substance content (separating agent content) is preferably adjusted to 0.5 to 5% by weight.

During separation, the solution is added to the crude oil (on-site), preferably by means of a feed vibrator. Separation then proceeds already at the temperature of the newly mined water-in-oil emulsion at a rate that allows the emulsion to be separated on its way to the finishing unit. The emulsion is then separated into refined oil and brine in a suitable separator, optionally heated, optionally using an electric field. The separating agent is added to the crude oil emulsion in an amount of 1 to 1000 ppm, preferably 10 to 100 ppm, based on the weight of the emulsion to be separated.
m at a temperature of 20-80°C.

The rapid separation agents used according to the invention can be used for water-in-oil emulsions with a brine content of about 0.1 to 9% by weight. Oils that can be rapidly dehydrated in this way include crude oil emulsions of various origins, such as those from northern Germany, northwest Germany, the Soviet Union, South America, Africa, the Middle East, and others. The separation proceeds very rapidly and almost quantitatively in the temperature range mentioned without the supply of additional heat.

Even when treatment agents have to be added in unfavorable cases,
It separates within a few minutes, but within 1-2 hours at most. The following examples relate to the production of emulsion separating agents and their use. (4) Production of component A Oxyalkylated isoalkylphenol formaldehyde resin I condensation 1030 parts (5 equivalents) of isooctylphenol were added to 4 (
xylol 0. Then, 50 g of a 30% aqueous formaldehyde solution (approximately 5 equivalents) was added over 1.5 hours.

0.04 parts by volume of concentrated hydrochloric acid (a). After addition of 3 parts of a powdered alkylaryl sulfonate, for example dodecylpenzole sulfonate, the mixture is heated to the boil for 5 hours under reflux cooling. Water containing hydrochloric acid after 7 hours 47
- is separated, the temperature being raised to 150°C.

Yield: 18 (1) parts, acid value, hydroxyl value: 30
2 (180-320 depending on the degree of condensation), η: 84.5C
P (measured using a falling ball viscometer according to Hepler at 200C on a 50% solution in xylol).

The resin thus obtained has 4 to 6 penzole nuclei per molecule.

■ Oxyethylation 12 parts of this isooctylphenol formaldehyde resin in xylol (75 parts of 100% product) are mixed with 0.65 parts of caustic soda (0.5% by weight on resin) in portions with 7 parts of ethylene oxide in a stirred autoclave. React for 3 to 5 hours at a pressure of 2.5 to 7 gauge atmospheres.

195 parts of a medium brown viscous product (theoretical: 197
part) is obtained as a 74% by weight solution in xylol.
Acid number of 100% product: 0, Hydroxyl number of 100% product: 120-13° η: 16.5 CP (measured on a 50% solution in xylol).

The compound thus obtained has 4
．． It has 6 alkylene oxide units.

(B) Preparation of component B having about 10 C@ repeating propylene oxide units (two-step process) 1st step (thermal reaction) Polyethylene having about 1 (4) repeating ethyleneimine units Imine 172y (2 molar equivalents) was charged as a 50% aqueous solution into a 2A stirred autoclave, and propylene oxide 116y (
2 mol) is injected little by little at 90 to 100C.

Time: 3 hours, pressure 26 gauge atmospheric pressure, temperature: 90-10
0℃. Next, 100℃/15~20T! Water is distilled off in NHg. 2nd stage (catalytic reaction) 15.6y (0.15 mol) of product from stage 1 and 0.62 KOH powder
4f (4% by weight relative to the product of step 1) together with V2A
Then, propylene oxide 687f (11.85 mol) was added little by little to 135 mol of propylene oxide.
℃, and ethylene oxide 132y (3 mol) is introduced in small portions at 125℃≦.

- Stir for 4 hours until the pressure is constant.

The product obtained can be used as is.

It consists of polyethyleneimine additionally containing about 80 moles of propylene oxide and about 2 moles of ethylene oxide. -) Use as separation agents Components A and B were tested alone and in a mixture of 5% by weight each of A and B on petroleum of various origins.

In this case, a certain Ppm amount of separating agent was added to the sample under stirring and then allowed to stand. The amount of water separated was recorded at regular time intervals, for example after 10 minutes, 2nd and 3rd pour, respectively. Finally, the remaining amounts of salt, water, and emulsion in the liquid phase were measured by a known method. In order to desalinate oils fed to the refinery containing only small amounts of emulsion or water, the following procedure was carried out.

Claims (1)

Claims: 1. 25 to 75% by weight, based on the active ingredient, of oxyethylated and/or oxypropylated products of isoalkylphenol formaldehyde resins, each containing 4 to 50 alkylene oxide units. oxyalkylate group having p
(contains 3 to 30 benzene nuclei with an isoalkyl group having 8 to 12 carbon atoms attached to the - position) (
A) and 75 to 25% by weight of at least one polyalkylene polyamine completely oxyalkylated by a factor of 10 to 200 in each case on the nitrogen atoms having at least two repeating alkylene imine units in the molecule (
Petroleum emulsion separating agents based on oxyalkylated compounds containing B) as active ingredient. 2. Petroleum emulsion separating agent according to claim 1, wherein component B is present in completely quaternized form. 3 The oxyalkylated alkylphenol formaldehyde resin (component A) has the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, x is an integer of 8 to 12, n is an integer of 2 to 3, and y is An integer from 4 to 50, and z is 3 to 3
The petroleum emulsion separating agent according to claim 1 or 2, which has an integer of 0).