CN1052094A - Organic bentonite gelatinizer and preparation method thereof - Google Patents

Abstract

A kind of organic clay gelifying agent and preparation method thereof.Gelifying agent of the present invention is made of hydrogen type bentonite and quaternary amine or quaternary amine and tertiary amine mixture insulating covering agent, its preparation method: earlier wilkinite is made hydrogen type bentonite by the method for ion-exchange, react with insulating covering agent under certain condition then, can make desired product.Organic bentonite gelatinizer of the present invention can be used as grease thickener, the anti-sedimentation agent of paint and thickening material, petroleum drilling oil-base mud and releasing stuck agent etc.

Description

Organic bentonite gelatinizer and preparation method thereof

The invention belongs to the organic clay gelifying agent, more particularly, is a kind of by wilkinite and quaternary amine or quaternary amine and topped dose of gelifying agent that constitutes of tertiary amine mixture and preparation method thereof.

Wilkinite is a kind of of clay, and its major ingredient is a montmorillonite, belongs to the moisture aluminosilicate mineral of laminate structure.Because itself has the commutative feature of positively charged ion, therefore can make the organobentonite of different series by required purposes.If organic cation contains the above alkyl group of 10 carbon atoms, the organobentonite that obtains will have the character of the formation gel that expands in some organic liquid, therefore organobentonite is often used as grease thickener, the auxiliary agent of coating, the anti-sedimentation agent and the thickening material of paint, petroleum drilling releasing stuck agent etc.

Usually prepare the bentonite method, at first wilkinite is modified as sodium type wilkinite, add quaternary amine then, stir time enough down, quaternary amine and wilkinite are fully reacted at 40-80 ℃, make it fully attached to the end face of wilkinite crystalline-granular texture, then after filtration, washing, dry, pulverize (or spraying drying), just can obtain required product (R.E.Grim, Clay mineralogy, second edition, 1968).

In recent years, for obtaining to have the organic clay gelifying agent of better gellifying property, many improvement on preparation technology, have been carried out.The USP4664842 Patent publish less than 25% sodium type bentonite slurry, is pumped to solid content in the homogenizer, carries out high speed shear then, applies enough energy, its particle is dissociated after, obtain organic clay with the quaternary amine reaction again.The GB2179336 patent is introduced, and will contain 4% the bentonitic slurries of sodium type earlier, shears certain hour in the homogenizer of the about 27.6MPa of pressure, and the energy that is applied to bentonite slurry is 1 * 10 ⁵More than the dried wilkinite of Jiao/kilogram, obtain the clay of fine grain high energy surface,, and then reactant is about at pressure continues in the homogenizer of 27.6MPa to shear for some time, make the energy that is applied on the mixture 4 * 10 again with the quaternary amine mixture reaction ⁵More than the dried wilkinite of Jiao/kilogram, the organophilic clay that obtains has good gellifying property.

As can be known above-mentioned, no matter be to adopt first high speed shear to react again, or shear reaction more earlier, continue method then to the reactant re-shearing, though can both improve gellifying property, all high-speed shearing equipment to be arranged, correspondingly increased the production cost and the process cost of organic clay.

The purpose of this invention is to provide a kind of have a good gellifying property contain the bentonitic gelifying agent of Hydrogen.

Another object of the present invention provides a kind of high speed shear that do not need, and only adopts the method for preparing organic bentonite gelatinizer of general whipping device.

Gelifying agent provided by the invention is to be made of hydrogen type bentonite and quaternary amine or quaternary amine and topped dose of institute of tertiary amine mixture, its preparation method is to convert wilkinite to hydrogen type bentonite earlier, under certain conditions, make the mixture reaction of itself and quaternary amine or quaternary amine and tertiary amine can make required organic bentonite gelatinizer.

The present invention prepares the technological process of bentonite gelatinizer:

(1) preparation hydrogen type bentonite: cation exchange capacity is restrained wilkinites greater than 75 milligramequivalents/100, add deionized water, be made into the slurries of solid content 5-15%, add and be selected from any acid in phosphoric acid, nitric acid, sulfuric acid, the hydrochloric acid (add-on is bentonitic 1-15 times), or adding h type resin (add-on is bentonitic 10-15 times), make at normal temperatures its reaction 4-8 hour, to PH be 2-3, promptly obtain the hydrogen type bentonite slurries;

(2) hydrogen type bentonite is made into the suspension that solid content is 1-6%, be heated to 40-80 ℃ after, add consumption and be topped dose of 35-100 gram/100 gram hydrogen type bentonites, continue to stir 2-4 hour, obtain floccular organobentonite.

(3) floccular organobentonite is filtered, wash with water then to no chlorion, be dried to water content≤3.5% below 105 ℃, through pulverizing or spraying drying, promptly get required gelifying agent, it forms content (with the gelifying agent is benchmark, heavy %): hydrogen type bentonite 50-70%, topped dose of 30-50%.

Used topped dose of the present invention is the quaternary amine or the mixture of quaternary amine and tertiary amine, the mixture of quaternary amine and tertiary amine preferably, when adopting quaternary amine and tertiary amine mixture, it forms content, and (with topped is benchmark, heavy %): quaternary amine 85-96%, tertiary amine 4-15%, quaternary amine 90-96% preferably, tertiary amine 4-10%.

Described quaternary amine, its molecular formula:

In the formula: R ₁Saturated or unsaturated alkyl for 10-24 carbon atom;

R ₂Or R ₃Be the alkyl of 1-24 carbon atom or the aromatic hydrocarbons of 7-10 carbon atom;

R ₄Be the alkyl of 1-6 carbon atom or the aromatic hydrocarbons of 7-10 carbon atom;

M ^-Comprise Cl ^-, Br ^-, I ^-, OH ^-, CH ₃COO ^-

The quaternary amine that the present invention uses comprises trimethylammonium hydrogenated tallow ammonium chloride, dimethyl benzyl hydrogenated tallow ammonia chloride, dimethyl hydroxyethyl hydrogenated tallow ammonium chloride, trimethyldodecane base amine bromide, methyl trioctylphosphine ammonium chloride, trimethylammonium docosane ammonium chloride, preferably trimethylammonium hydrogenated tallow ammonia chloride and dimethyl benzyl hydrogenated tallow ammonia chloride.These quaternary amines are the commercially available prod.

Described tertiary amine, its molecular formula:

In the formula: R ₁Full or the unsaturated alkyl of 12-14 carbon atom;

R ₂And R ₃Alkyl or its mixture for 1-24 carbon atom;

The tertiary amine that the present invention uses comprises dimethyl hydrogenation tallow amine, dimethyl lauryl amine, methyl-benzyl hydrogenated tallow amine, preferably dimethyl hydrogenation tallow amine.These tertiary amines are the commercially available prod.

The present invention compared with prior art has following advantage:

1. because the present invention adopts the hydrogen type bentonite of remodeling, improved gelation, made its gel in organic solution have higher viscosity and mineral oil is had stronger thickening ability.

2. the present invention does not need high-speed shearing device, only needs a general whipping device just can satisfy processing requirement, make easy to operate, the process cost reduction.

3. adopt the more cheap tertiary amine compound of part, thereby reduced production cost.

Organic bentonite gelatinizer of the present invention has good gellifying property, can be used as grease thickener, the anti-sedimentation agent of paint and thickening material, petroleum drilling oil-base mud and releasing stuck agent etc.

Organic bentonite gel ability of the present invention is weighed by organobentonite-solvent system kinetic viscosity value, concrete measuring method:

Take by weighing 3.6 gram organobentonite samples, put into the container that band stirs, add 36 milliliters of synthetic thinners (commercially available), stir 5 minutes (rotating speed is about 1500 rev/mins), add 1.5 milliliters of ethanol (ethanol/water is 95/5), stirred 10 minutes, and added 18 milliliters of synthetic thinners again, continue to stir 5 minutes; Take out mixture and measure kinetic viscosity (rotating speed is 750 rev/mins) with NDJ-79 type rotational viscosimeter immediately.

Cation exchange capacity analytical procedure of the present invention is to adopt ammonium acetate drip-rinsing process (Inst. of Forestry and Soil, Chinese Academy of Sciences, soil conventional method of analysis, P69,1970).

Further specify characteristics of the present invention with example below.

Example 1

This example is the preparation hydrogen type bentonite.

After the dried wilkinite pulverizing of 120 grams, add 2 liters of deionized waters, being made into solid content is 6% slurries, gravel is removed in filtration, sedimentation then, adds 2.5 kilograms of h type resins, stirs at normal temperatures 8 hours, to PH be 2-3, remove by filter resin at last, promptly obtain the hydrogen type bentonite slurries.

Example 2

Getting solid content is 4 liters in 2.5% hydrogen type bentonite slurries, under agitation be heated to 80 ℃, add 11.3 gram trimethylammonium hydrogenated tallow ammonia chlorides, 1.7 gram dimethyl hydrogenation tallow amine continues to stir 2 hours, reaction finishes after-filtration, and be washed to no chlorion, dry below 105 ℃ to water content less than 3.5%, with pulverizer solid is crushed to 200 orders again, the oyster white organobentonite.It is 2700 * 10 that this product gel ability records kinetic viscosity by aforesaid method ^-3Handkerchief second.

Example 3

This example is the organobentonite product that different topped dosimetric systems gets.

Preparation process is with example 1.Topped dose of consumption: trimethylammonium hydrogenated tallow ammonia chloride 63 grams, dimethyl hydrogenation tallow ammonium 7.0 grams, it is 4200 * 10 that the product that makes records kinetic viscosity by preceding method ^-3Handkerchief second.

Example 4

The organobentonite property comparison example of this example for making with hydrogen type bentonite and sodium type wilkinite.

1. getting solid content is 4 liters in 2.5% hydrogen type bentonite slurries, under agitation be heated to 80 ℃, add 140 gram trimethylammonium hydrogenated tallow ammonium chlorides, continue to stir 3 hours, filter then, be washed till no chlorion with deionized water, dry below 105 ℃ to moisture content be 2.0%, with pulverizer solid is crushed to 200 orders again, gets oyster white organobentonite A.

2. make organobentonite B by example 3.

3. getting solid content is 4 liters of 2.5% sodium type bentonite slurries, under agitation be heated to 80 ℃, add 140 gram trimethylammonium hydrogenated tallow ammonium chlorides, continue to stir 4 hours, filter then, behind deionized water wash, 105 ℃ of following temperature dry to moisture content be 2.5%, with pulverizer solid is crushed to 200 orders again, gets oyster white organobentonite C.

Above-mentioned two types organobentonite performance sees Table 1.

The organobentonite performance that table 1 is two types relatively

Sample	Original soil	Organobentonite-synthetic thinner gel kinetic viscosity, handkerchief second
			A B C	Hydrogen soil Hydrogen soil sodium type soil	2500×10 －34200×10 －3400×10 －3

As seen from table, the gelifying agent by the hydrogen type bentonite preparation has gellifying property preferably.

Example 5

This example is for the organobentonite of the present invention preparation and be used separately as the performance comparison of grease thickener with the organobentonite of sodium type wilkinite preparation.

1. with the method for example 2, mix to make organobentonite D in 2 hours with hydrogen type bentonite with 80.0 gram trimethylammonium hydrogenated tallow ammonia chlorides and 5.8 gram dimethyl hydrogenation tallow amines.

2. with the method for example 2, mixed with hydrogen type bentonite 3 hours, make organobentonite E with 140 gram trimethylammonium hydrogenated tallow ammonia chlorides.

3. adopt the method for example 2, mixed 4 hours with sodium type wilkinite, make organobentonite F with 76.0 gram dimethyl benzyl hydrogenated tallow ammonia chlorides.

Above-mentioned organobentonite is made lubricating grease as follows:

1. 20 gram organobentonites are added in the 100 gram lubricating oil, 2000 rev/mins rotating speed down cuts 5 minutes;

2. add 6 gram acetone and make dispersion aids, continue to shear 10 minutes;

3. add 80 gram lubricating oil at last, shear and to make lubricating grease in 10 minutes.

Different organobentonites sees Table 2 to the influence of PERFORMANCE OF GREASES.

The different organobentonites of table 2 are to the influence of PERFORMANCE OF GREASES

Project	Organobentonite			Measuring method
					D	E	F
	1/4 penetration degree, 60 times, 1/10 millimeter cylinder stability, 2 hours, room temperature, 1/10 millimeter Stencil oil-dividing, 100 ℃, 24 hours, the % corrosion, 100 ℃, 24 hours	62 75 0.99 ／	53 86 3.67 is qualified					66 120 3.95 is qualified	GB5017 GB2359 ZBE36016-88 GB7326

Table 2 data show that the PERFORMANCE OF GREASES of using organobentonite of the present invention to make viscosifying agent is better than doing with the organobentonite of sodium type wilkinite preparation the PERFORMANCE OF GREASES of viscosifying agent.

Claims (7)

1, a kind of organic bentonite gelatinizer and preparation method thereof, it is characterized in that it is made up of hydrogen type bentonite and quaternary amine or quaternary amine and topped dose of institute of tertiary amine mixture, it forms content, and (with the gelifying agent is benchmark, heavy %): hydrogen type bentonite is 50-70%, and topped dose is 30-50%, when being quaternary amine and tertiary amine mixture as if topped dose, it forms content, and (with topped dose is benchmark, heavy %) be quaternary amine 85-96%, tertiary amine 4-15%, the preparation method of gelifying agent:

(1) preparation hydrogen type bentonite: cation exchange capacity is restrained wilkinites greater than 75 milligramequivalents/100, add deionized water, be made into the slurries of solid content 5-15%, add acid then, add-on is bentonitic 1-15%, or adds h type resin, add-on is bentonitic 10-15 times, reacted at normal temperatures 4-8 hour, to PH be 2-3, promptly obtain the hydrogen type bentonite slurries;

(2) hydrogen type bentonite is made into the suspension that solid content is 1-6%, be heated to 40-80 ℃ after, add consumption and be topped dose of 35-100 gram/100 gram hydrogen type bentonites, continue to stir 2-4 hour, floccular organobentonite;

(3) floccular organobentonite is crossed the Lu, wash with water then, be dried to water content≤3.5% below 105 ℃,, promptly get required gelifying agent through pulverizing or spraying drying to no chlorion.

2, in accordance with the method for claim 1, it is characterized in that described quaternary amine molecular formula is:

In the formula: R ₁Saturated or unsaturated alkyl for 10-24 carbon atom;

R ₂, R ₃Be the alkyl of 1-24 carbon atom or the aromatic hydrocarbons of 7-10 carbon atom;

R ₄Be the alkyl of 1-6 carbon atom or the aromatic hydrocarbons of 7-10 carbon atom;

M ^-Comprise Cl ^-, Br ^-, I ^-, OH ^-, NO ^- ₃, CH ₃COO ^-

3, according to claim 1,2 described methods is characterized in that quaternary amine preferably trimethylammonium hydrogenated tallow ammonia chloride and dimethyl benzyl hydrogenated tallow ammonia chloride.

4, in accordance with the method for claim 1, the molecular formula that it is characterized in that tertiary amine is:

In the formula: R ₁Saturated or unsaturated alkyl for 12-24 carbon atom;

R ₂, R ₃Alkyl or alkyl mixture for 1-24 carbon atom.

5, according to claim 1,4 described methods is characterized in that preferably dimethyl hydrogenation tallow ammonium of tertiary amine.

6, in accordance with the method for claim 1, it is characterized in that the described topped dose of mixture of quaternary amine and tertiary amine preferably, its form content (with topped dose be benchmark, heavy %) quaternary amine 90-96% preferably, tertiary amine 4-10%.

7, in accordance with the method for claim 1, it is characterized in that described acid can be selected from any acid of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid.