CN1048999C - Filtering-loss reducing agent of humic resin and its prepn - Google Patents
Filtering-loss reducing agent of humic resin and its prepn Download PDFInfo
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- CN1048999C CN1048999C CN94113858A CN94113858A CN1048999C CN 1048999 C CN1048999 C CN 1048999C CN 94113858 A CN94113858 A CN 94113858A CN 94113858 A CN94113858 A CN 94113858A CN 1048999 C CN1048999 C CN 1048999C
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Abstract
The present invention relates to a humic acid resin class filtering reduction and loss agent used as a well drilling mud treatment agent and a preparation method thereof. The filtering reduction and loss agent comprises humic acid active intermediates, water-soluble polyacrylonitrile ammonium salt copolymer and water-soluble carbamide resin. A non-deslagging technological line of a one-step method or a two-step method is adopted by the preparation method. The filtering reduction and loss agent has the advantages of great production strength, high raw material utilization rate, no secondary pollution formation, good temperature resistance and good salt resistance, which is widely suitable for deep wells of freshwater, salt water and medium salt pollution.
Description
The invention belongs to additive for drilling fluid, relate in particular to a kind of humic resin fluid loss agent and preparation method thereof.
(US 3 for the seventies United States Patent (USP), 956,140) once reported by synthetic polymer filtrate reducers such as phenol, urea, formaldehyde, sulphite and other modification component ultrapas, salicylic acid, phenylformic acid, phthalic acids, yet, synthetic method and straight polymer add the water management condensation course because existing, this condensation course is difficult to control, and have shortcomings such as cost height, heat-resisting property difference, and in fact be not used widely.The Resinex (fluid loss agent) of U.S. Magcobar company is the product that is made up by brown coal and sulfonated phenol formaldehyde resin (SMP), and this product is better than simple polymkeric substance synthetic fluid loss agent heat-resisting property, and cost also descends to some extent.
The eighties, the valchovite filtrate reducer for drilling fluid such as the Chinese patent " a kind of novel treating agent of drilling mud that contains humic acids and preparation method thereof " (patent No. 85106524) of China's development, this patent is to be raw material with sulfomethylation Sodium salts humic acids, sulfonated-pheno-formoldehyde resin and sulphur methyl hydrolyzed polyacrylonitrile, through brown coal normal pressures extracting → sedimentation deslagging → evaporation concentration, the operational path that carries out graft polymerization with resol after sulfonation makes product again.Though its product performance have surpassed the Resinex of the U.S., also exist raw material sources to be subjected to strict restriction, raw material availability is not high, the shortcoming of the higher and secondary pollution that the sedimentation deslagging causes of cost.
The purpose of this invention is to provide a kind of humic resin fluid loss agent of cheapness and be not subjected to the raw material coal to limit and do not cause the preparation method of secondary pollution.
Humic resin fluid loss agent of the present invention consists of humic acids (HA) active intermediate, multiple polymers of water-soluble polypropylene nitrile ammonium salt and water-soluble carbon amide resins, and its each component weight percentage is:
Humic acids (HA) active intermediate 15-70%
The multiple polymers 5-40% of water-soluble polypropylene nitrile ammonium salt
Water-soluble carbon amide resins 10-50%;
Described humic acids (HA) active intermediate is:
A. with the weathered coal humic acids (HA) active intermediate that raw material is applicable to the fluid loss agent of salty mud, consist of humic acids (HA) active intermediate content greater than 35% weathered coal, water, highly basic, strong oxidizer, sulfide, sulphonating agent and formaldehyde, its each component content is:
Weathered coal 1 water 2-5 strong oxidizer 0.01-0.1
Sulfide 0.005-0.05 highly basic 0.07-0.25 sulphonating agent 0.03-0.15
Formaldehyde 0-0.25
Wherein highly basic is a kind of or composition in potassium hydroxide, the sodium hydroxide, and strong oxidizer is one or more mixtures in alkali metal permanganate, heavy complex acid salt, oxymuriate, hydrogen peroxide, the persulphate; Sulfide is one or more mixtures in ferrous sulfate, the alkali metalsulphide Containing Sulfur ammonium, and sulphonating agent is S-WAT, sodium bisulfite, ammonium sulphite, one or more mixtures in the Sodium Metabisulfite;
B. be humic acids (HA) active intermediate of the raw material fluid loss agent that is applicable to fresh water less salt mud with the weathered coal, consist of humic acids (HA) content greater than 35% weathered coal and highly basic and water, its component content (weight ratio) is:
Weathered coal 1 water 2-5 highly basic 0.07-0.20
Wherein highly basic is a kind of or its mixture in potassium hydroxide, the sodium hydroxide;
C. consisting of humic acids (HA) content with brown coal, humic acids (HA) active intermediate when peat is raw material greater than coal, water, highly basic, sulphonating agent, its each component content (weight ratio) of formaldehyde of 35% is:
Coal 1 water 2-5 highly basic 0.08-0.25
Sulphonating agent 0.03-0.20 formaldehyde 0-0.35
Wherein coal can be brown coal, peat or their oxygen hydrolysis products, and highly basic is a kind of or composition in potassium hydroxide, the sodium hydroxide; Sulphonating agent is S-WAT, sodium bisulfite, ammonium sulphite, one or more mixtures in the Sodium Metabisulfite.
The multiple polymers of described water-soluble polypropylene nitrile ammonium salt consists of water-soluble polypropylene acyl ammonium salt, water and additive, and its component content (weight ratio) is:
Water-soluble polypropylene nitrile ammonium salt 1 water 0.1-6 additive 0.05-0.45
Wherein additive can be that polyacrylamide is by one or more mixtures in (PAM), sulfomethylation polyacrylamide (SPAM), carboxymethyl cellulose, Natvosol, polyoxyethylene glycol, polyvinyl alcohol, polyoxyethylene phenol ether, the borax.
Described water-soluble carbon amide resins consists of carbonyl amines, formaldehyde, sulphonating agent, highly basic, water, and its component content (weight ratio) is:
Carbonyl amines 1 highly basic 0.005-0.03
Formaldehyde 0.5～2.5 water 0.1～1
Sulphonating agent 0.05～1
But the wherein complex compound of Fe, the Al of carbonyl amines carbon neutral acid amides, methylol carboxamide, carboxamide, Zn, Mn, Ti, Zr, Hf and one or more mixtures in the uride, but one or more mixtures in the sulphonating agent S-WAT, sodium bisulfite, ammonium sulphite, Sodium Metabisulfite; Highly basic can be a kind of or its mixture in sodium hydroxide, the potassium hydroxide.
Preparation method of the present invention is as follows:
1.HA the preparation of active intermediate
(1) be that feedstock production is when being suitable for product with salty mud with the weathered coal
A. form the content weighing by the HA active intermediate of above-mentioned A;
B: add entry in weathered coal, strong oxidizer was 80-160 ℃ of reaction 0.5-6 hour;
C: the reaction back added sulfide, in 80-140 ℃ of reaction 0.5-3 hour;
D: reaction back adding highly basic, sulphonating agent, formaldehyde obtained the HA active intermediate in 1-5 hour 100～180 ℃ of reactions.
(2) be that feedstock production is when being applicable to fresh water less salt (NaCl≤4%) type mud system product with the weathered coal
A: by the HA active intermediate component content weighing of above-mentioned B;
B: in weathered coal, add entry, highly basic and obtained the HA active intermediate in 0.5-3 hour in 30-150 ℃ of reaction.
(3) with brown coal, when peat is raw material
A: by the HA active intermediate component content weighing of above-mentioned C;
B: in brown coal or peat, add entry, highly basic in 30-150 ℃ of reaction 0.5-3 hour;
C: the reaction back adds sulphonating agent, formaldehyde obtained the HA active intermediate in 0.5-5 hour 100-160 ℃ of reaction.
2. the preparation of the multiple polymers of water-soluble polypropylene nitrile ammonium salt
A. by the multiple polymers component content weighing of above-mentioned water-soluble polypropylene nitrile ammonium salt;
B: water is mixed with water Jie polyacrylonitrile ammonium salt with additive, and reaction got final product in 0.2-2 hour under 20-100 ℃.
3. the preparation of water-soluble carbon amide resins
A. press the component content weighing of above-mentioned water-soluble carbon amide resins;
B. each component is mixed, get final product in the time of on 50-150 ℃ of reaction 0.5-4;
(4) synthetic fluid loss agent
(1) a. forms the content weighing with the product that 1,2,3 steps make by described humic resin fluid loss agent;
B. the product that 1,2,3 steps are made adds simultaneously in the reactor boiling off moisture content under the 100-160 ℃ of temperature after reaction in 16 hours and gets solid phase prod;
(2) a. makes the component content weighing of product by described water-soluble carbon amide resins by forming humic resin fluid loss agent component content forming 2,3 steps;
B. 2,3 steps being prepared required component adds simultaneously by boiling off moisture content and get solid phase prod after reaction in 1-6 hour under the 100-160 ℃ of temperature in 1 intermediate that makes.
Humic resin fluid loss agent of the present invention is made into through North China Oilfield the 3rd mud plant of drilling engineering company, Daqing oil field drilling well one company and contains 7% bentonite base slurry, and the salient features that records is as follows: sample and the dehydration of dosage condition determination AV PV YP gel strength API dehydration High Temperature High Pressure
(lmin) (W/V) 100 ℃/h (mPa.s) (mPa.s) (Pa) (Pa) ml ml/30min * 2 fresh water bases slurry * R, T 29.5 3 26.5 10 25-
180/16 → RT, 35 5 30 25 25SCUR R, T 22 18 40 9.2-3% fresh water 180/16 → RT 15 12 30 8.5 24SCUR 5% R, T 27 13 14 25 8-10% NaCl 180/16 → RT 19 10 66 12 32SCUR 5% R, T 25.5 17 8.5 18 8.5-15%NaCl, 180/16 → RT 16 797 12.5 35
* R, T---room temperature; AV---apparent viscosity; YP---yield value;
PV---plastic viscosity; SCUR---be the code name of fluid loss agent of the present invention.
The advantage of humic resin fluid loss agent of the present invention is as follows:
1. adopt not deslagging technology, production intensity is big, and the raw material availability height does not form for the second time and pollutes, and cost is low, and is profitable;
2. to soak performance good for high temperature resistance, anti-salt;
3. fall leak-off and tackify not, have concurrently and improve the rheological function;
4. the mud cake quality densification of Xing Chenging is smooth, and the hole diameter rule helps protecting well, stabilizing borehole;
5. be widely used in the deep-well under fresh water, salt water, middle salt (10-15% sodium-chlor) pollution;
6. compatibleness is good, can be made into recombiner with other treatment agent and use, and promotes action effect, reduces the drilling well comprehensive cost.
Embodiments of the invention are as follows:
Embodiment 1
(1) adds weathered coal 10g, KMnO in the reactor
40.15g, water 30g, 80 ℃ were reacted 0.5 hour, added Na
2S 0.1g continues reaction 0.5 hour, adds NaOH 0.8g, Na
2SO
30.25g, NaHSO
30.2g, formaldehyde 1.2g, 130 ℃ of reactions of sulfonation temperature obtained the HA active intermediate in 1.2 hours.
(2) add 4.5g water Jie polyacrylonitrile ammonium salt in the reactor, water 14g, 20～30 ℃ of reactions of additive 0.2g SPAM (sulfomethylation polyacrylamide) and 0.22g carboxymethyl cellulose 0.5 hour obtain the multiple polymers of water-soluble polypropylene nitrile ammonium salt.
(3) add 2.6g carboxamide, NaHSO in the reactor
30.2g, formaldehyde 3g, NaOH 0.03g, water 3.5g, 70 ℃ of reactions obtained the water-soluble carbon amide resins in 1.2 hours.
(4) with above-mentioned (1), (2), (3) intermediate material disposable throw in reactor, to be blended under 130 ℃ after reaction in 4 hours, be evaporated to the dried solid phase prod that obtains.
Embodiment 2
KMnO with (1) in the example 1
4Change 0.3g into, 150 ℃ were reacted Na 2 hours
2S changes 100 ℃ of reactions of 0.07g 0.5 hour into, and sulfonation temperature changes 140 ℃ into, and all the other are with example 1.
The polyacrylonitrile ammonium salt of (2) changes 2.5g in the example 1, and additive SPAM changes PAM 0.2g into, and all the other are with example 1.
The preparation of (3) is with example 1 in the example 1.
The reaction conditions of (4) changes 100 ℃ in the example 1, reaction in 5 hours, and all the other are with example 1.
Embodiment 3
Change the preparation NaOH of (1) in the example 1 into 1.5g, Na
2SO
3Change 0.4g, NaHSO
30.3g formaldehyde is 1.7g, sulfonation reaction is 135 ℃, and 2 hours all the other are with example 1.
Condition by (2) in the example 1 prepares the multiple polymers of hydrolyzed polyacrylonitrile ammonium salt.
Condition by (3) in the example 1 prepares the water-soluble carbon amide resins.
In the example 1 temperature of reaction of (4) change into 140 ℃ 3.5 hours, all the other are with example 2.
Embodiment 4
(1) adds weathered coal 10g in the reactor, water 40g, strong oxidizer KMnO
40.2g and Na
2Cr
2O
7.2H
2O 0.01g, 160 ℃ were reacted 1.5 hours, and then added Na
2120 ℃ of reactions of S 0.13g 0.5 hour.Add NaOH 1.8g, Sodium Metabisulfite 0.5g, 145 ℃ of reactions of formaldehyde 0.85g obtained the HA active intermediate in 3 hours.
(2) add 2g water Jie polyacrylonitrile ammonium salt in the reactor, water 9g, additive PAM0.17g, borax 0.06g, polyoxyethylene phenol ether 0.15g, 50 ℃ of reactions got the multiple polymers of hydrolyzed polyacrylonitrile amine salt in 40 minutes.
(3) add 3.75g methylol carboxamide in the reactor, Sodium Metabisulfite 2g, formaldehyde 8.5g, NaOH0.1g, water 1.2g, 120 ℃ of reactions obtained the water-soluble carbon amide resins in 1 hour 10 minutes.
(4) will above-mentioned (1), (2), mix in the disposable input reactor of (3) intermediate material, 150 ℃ of reactions after 6 hours evaporation anhydrate solid phase prod.
Embodiment 5
Change the strong oxidizer of (1) in the example 4 into ammonium persulphate 0.3g, reaction be 130 ℃ 2.5 hours, then with Na
2S changes FeSO into
4.7H
2O 0.5g, 110 ℃ the reaction 50 minutes, add then NaOH 1.4g all the other with example 4.
The preparation additive of (2) changes carboxymethyl cellulose 0.25g in the example 4, polyoxyethylene glycol 0.1g, be reflected at 40 ℃ 20 minutes, all the other are with example 4.
In the example 4 the preparation methylol carboxamide of (3) change into carboxamide manganese complex 4g all the other with example 4.
In the example 4 synthetic reaction condition of (4) be 160 ℃ 2 hours, all the other are with example 4.
Embodiment 6
Change (1) oxygenant in the example 4 into H
2O
21g, all the other are with example 4.
(2) middle hydrolyzed polyacrylonitrile ammonium salt changes 1.5g in the example 4, and additive changes polyvinyl alcohol 0.3g into, Natvosol 0.2g, and all the other are with example 4.
(3) preparation is with example 4.
(4) synthesis condition changes 120 ℃, and 4 hours all the other are with example 4.
Embodiment 7
The oxygenant of (1) changes Potcrate 0.25g, KMnO in the example 4
40.1g, reaction conditions change into 130 ℃ 3 hours, then add Na
2S 0.14g reaction conditions is 125 ℃, reacts 1 hour, and all the other are with example 4.
The additive of (2) changes polyoxyethylene phenol ether 0.2g in the example 4, carboxymethyl cellulose 0.5g, and all the other make the multiple polymers of water Jie polyacrylonitrile ammonium salt with example 4.
The carbonyl amines of (3) changes ureide 2.8g in the example 4, and sulphonating agent changes NH into
4SO
32.5g, the reaction change into 150 ℃ 0.5 hour, all the other are with example 4.
The synthetic reaction condition of (4) changes 145 ℃ into 4.5 hours all the other is with example 4 in the example 4.
Embodiment 8
Obtain behind the HA active intermediate forming in the intermediate that the then disposable adding of each component materials of weighing obtains by (1) by the preparation condition of (1) in the example 3 by the material in the preparation of (2), (3) in the example 4, in 140 ℃ evaporate through 4 hours reaction backs anhydrate solid phase prod.
Embodiment 9
(1) adds weathered coal 10g, water 50g, KMnO in the reactor
40.5g, add Na after 2 hours in reaction under 125 ℃
2S 0.18g, 90 ℃ were reacted down after 20 minutes, added NaOH 1.6g, Sodium Metabisulfite 0.45g, formaldehyde 0.75g obtained the HA active intermediate in 3 hours at 150 ℃ of following sulfomethylations.
(2) form each component materials of weighing by the material of the multiple polymers of (2) preparation water Jie's polyacrylonitrile ammonium salt in the example 7, material by preparation (3) in the example 4 is formed the weighing each component, in the HA active intermediate that disposable adding is obtained by (1), boiled off moisture content in 5.5 hours through 135 ℃ of reactions and get product.
Embodiment 10
The Sodium Metabisulfite of (1) changes 1.3g in the example 9, and formaldehyde is 2.3g, all the other the institute in steps condition with example 9.
Embodiment 11
(1) adds the 10g weathered coal in the reactor, 0.12g KClO
3, water 32g adds Na 120 ℃ of reactions after 2 hours
2S 0.04g, FeSO
4.7H
2100 ℃ of reactions of O 0.01g 0.5 hour add KOH 2g, HaHSO
30.3g, Sodium Metabisulfite 0.3g, formaldehyde 1.5g, 180 ℃ of reactions obtained the HA active intermediate in 1 hour 10 minutes.
(2) in the reactor that fills the HA active intermediate, add water Jie polyacrylonitrile ammonium salt 1.5g, SPAM0.2g, borax 0.15g, carboxamide 2.5g, Sodium Metabisulfite 1.7g, formaldehyde 4g, 115 ℃ were reacted 6 hours, and boiled off moisture content and obtain solid phase prod.
Embodiment 12
When just (3) in the example 4 being prepared the water-soluble carbon amide resins, the methylol carboxamide is changed into the methylol carboxamide complex compound 3.6g that contains 1%Fe or Al or Mn or Ti, its preparation method is to add in the aqueous solution of methylol carboxamide 20-40% that to calculate its metal ion content by respective metal salt (vitriol or muriate) be 1% corresponding salt, obtained corresponding complex compound in 0.5 hour in 50-80 ℃ of reaction, boil off moisture content and obtain solid carbon acid amides complex compound, all the other steps are with example 4.
Embodiment 13
Methylol carboxamide complex compound changes the complex compound that contains 2%Mn or Fe or Zn or Ti in the example 12, and its complex compound amount is 3.2g, and its preparation method is with example 12, and all the other steps are with example 12.
Embodiment 14
(1) add weathered coal 20g in the reactor, water 80g, NaOH 3g react down at 80 ℃ and made the HA active intermediate in 1 hour.
(2) add 7g water Jie polyacrylonitrile ammonium salt in the reactor, water 7g, carboxymethyl cellulose 0.35g, 30 ℃ of reactions obtained the multiple polymers of water Jie polyacrylonitrile ammonium salt in 0.5 hour.
(3) in reactor, add the 3g carboxamide, water 3g, NaHSO
31g, Sodium Metabisulfite 2g, NaOH 0.05g, formaldehyde 5.8g, 90 ℃ of reactions obtained the water-soluble carbon amide resins in 2 hours.
(4) the disposable throwing in reactor of intermediate that in the reactor (1), (2), (3) is obtained boils off moisture content 100 ℃ of reactions after 4.5 hours and gets solid phase prod.
Embodiment 15
(1) add weathered coal 15g in the reactor, water 45g, 100 ℃ of reactions of KOH 1.8g obtained the HA active intermediate in 40 minutes.The HA active intermediate that disposable adding after the each component weighing in (2), (3) is obtained by (1) by example 14 then, synthesis temperature be at 130 ℃, reacts to boil off moisture content after 3 hours and get solid phase prod.
Embodiment 16
The reaction conditions of (1) changes at 30 ℃ in the example 15, reacts 1 hour all the other step condition with example 15.
Embodiment 17
Synthesis temperature in the example 16 changes 140 ℃ of reactions 4 hours into, and all the other conditions are with example 16.
Embodiment 18
The temperature of (1) changes 120 ℃ in the example 16, and the reaction times is 45 minutes, all the other examples 16.
Embodiment 19
(1) reactor adds weathered coal 10g, water 30g, and 70 ℃ of reactions of NaOH 1.35g obtained the HA active intermediate in 1 hour.
(2) in the reactor that fills the HA active intermediate, add methylol carboxamide 3g, sodium bisulfite 1.2g, formaldehyde 4g, water Jie polyacrylonitrile ammonium salt 0.8g, PAM 0.22g, polyoxyethylene phenol ether 0.1g is in 150 ℃, reacts to boil off moisture content after 3 hours and obtain solid phase prod.
Embodiment 20
(1) prepares the HA active intermediate by (1) condition in the example 19.
(2) by the multiple polymers of example 4 (2) preparation water Jie polyacrylonitrile ammonium salts.
(3) by example 12 (3) preparation water-soluble carbon amide resinss.
(4) be blended in 120 ℃ with (1), (2), (3) are disposable in reactor, react and boil off moisture content after 3 hours and obtain solid phase prod.
Embodiment 21
(1) condition by (1) in the example 19 prepares the HA active intermediate.
(2) condition by (2) in the example 7 prepares the multiple polymers of water Jie polyacrylonitrile ammonium salt.
(3) condition by (3) in the example 13 prepares the water-soluble carbon amide resins.
(4) be mixed in 110 ℃ of reactions and be combined into product in 8 hours (1), (2), (3) intermediate are disposable in reactor, boil off moisture content and obtain solid phase prod.
Embodiment 22
(1) add weathered coal 15g in the reactor, water 50ml, NaOH 0.5g, 35 ℃ of reactions of KOH 2g obtained the HA active intermediate in 50 minutes.
(2) reactor adds water Jie polyacrylonitrile amine salt 5g, water 10ml, and polyvinyl alcohol 0.12g, polyoxyethylene glycol 0.1g, borax 0.05g, 40 ℃ of reactions obtained the multiple polymers of water Jie polyacrylonitrile ammonium salt in 40 minutes.
(3) add ureide 8.5g in the reactor, water 2.5g, NH
4SO
31g, Sodium Metabisulfite 1.5g, NaOH 0.03g, formaldehyde 25.5g, 120 ℃ of reactions obtained the water-soluble carbon amide resins in 0.5 hour.
(4) be mixed in 145 ℃ with (1), (2), (3) intermediate are disposable in reactor, react and boil off moisture content after 2.5 hours and obtain solid phase prod.
Embodiment 23
(1) brown coal 10g, water 40g, 80 ℃ of reactions of NaOH 1.4g 1 hour 10 minutes add Sodium Metabisulfite 0.8g, and formaldehyde 1.5g obtained the HA active intermediate in 2 hours in 130 ℃ of reactions.
(2) add 3g hydrolyzed polyacrylonitrile ammonium salt in the reactor, water 3g, 0.1gPAM (polyacrylamide), the 0.12g carboxymethyl cellulose, 25 ℃ of reactions obtained the multiple polymers of water Jie polyacrylonitrile ammonium salt in 0.5 hour.
(3) add the 2g carboxamide in the reactor, Sodium Metabisulfite 1.2g, water 2g, formaldehyde 3.2g, 60 ℃ of reactions of NaOH 0.01g obtained the water-soluble carbon amide resins in 1 hour 20 minutes.
(4) be blended in 120 ℃ with (1), (2), (3) intermediate are disposable in reactor, react and boil off moisture content after 4 hours and obtain solid phase prod.
Embodiment 24
(1) condition by example 23 (1) prepares the HA active intermediate.
(2) reactor adds hydrolyzed polyacrylonitrile ammonium salt 2g, water 7g, and 0.15g SPAM (sulfonated polyacrylamide), 0.12g polyoxyethylene phenol ether, the 0.05g borax obtained the multiple polymers of hydrolyzed polyacrylonitrile ammonium salt in 40 minutes in 30 ℃ of reactions.
(3) 3.6g methylol carboxamide in the reactor, 0.8 Sodium Metabisulfite, the 0.5g S-WAT, the 0.4g ammonium sulphite, NaOH 0.07g, water 3g, formaldehyde 4g, 100 ℃ of reactions obtained the water-soluble carbon amide resins in 40 minutes.
(4) intermediate product that (1), (2), (3) are made in reactor disposable be blended in 100 ℃ down reaction boil off moisture content after 6 hours and obtain solid phase prod.
Embodiment 25
(1) brown coal 10g, water 35g, NaOH 2g, 30 ℃ were reacted 0.5 hour, added sodium bisulfite 0.8g, and S-WAT 1.1g obtained the HA active intermediate in 1 hour 40 minutes 150 ℃ of reactions.
(2) prepare multiple polymers of water-soluble polyene nitrile ammonium salt and water-soluble carbon amide resins respectively by (2) in the example 24, (3), then, boil off moisture content 140 ℃ of reactions after 3 hours and obtain solid phase prod them and the HA intermediate that obtains by (1) disposable mixing in reactor.
Embodiment 26
Condition by (1) in the example 25 prepares the HA active intermediate, then in reactor, add hydrolyzed polyacrylonitrile ammonium salt 1.4g, PAM 0.3g, carboxymethyl cellulose 0.23g, polyoxyethylene glycol 0.1g, carboxamide 2.7g, ammonium sulphite 0.2g, Sodium Metabisulfite 1.3g, formaldehyde 2.8g boils off moisture content in 115 ℃ of reactions after 4.5 hours and obtains solid phase prod.
Embodiment 27
(1) example 25 (1) preparation in, increase formaldehyde 2.5g during sulfonation, all the other are with the condition of (1) in the example 25.
(2) add hydrolyzed polyacrylonitrile ammonium salt 2.5g in the reactor, water 10g, PAM 0.2g, Natvosol 0.15g, 50 ℃ of reactions obtained the multiple polymers of hydrolyzed polyacrylonitrile ammonium salt in 0.5 hour.
(3) add ureide 3.5g in the reactor, water 2.5g, ammonium sulphite 1g, sodium bisulfite 1.8g, formaldehyde 3.8g, NaOH 0.1g, reaction obtained the water-soluble carbon amide resins in 30 minutes under 145 ℃.
(4) intermediate that (1), (2), (3) are made boils off moisture content in 110 ℃ of reactions after 5 hours after the disposable mixing and obtains solid phase prod in reactor.
Embodiment 28
Change the brown coal of (1) in the example 23 into peat 10g, all the other all conditions are with example 23.
Embodiment 29
Change the brown coal in the example 27 into peat 10g, all the other all conditions are with example 26.
Embodiment 30
(1) brown coal 10g, water 35g, NaOH 1.7g, 120 ℃ were reacted 1.2 hours, added Sodium Metabisulfite 0.5g, formaldehyde 2.5g, 120 ℃ of reactions obtained the HA active intermediate in 0.5 hour.
(2) prepare the polyacrylonitrile ammonium salt composition content weighing each component of polymers again by (2) in the example 23, simultaneously in the HA intermediate that obtains by (1) by the disposable adding of composition content weighing each component of (3) preparation water-soluble carbon amide resins in the example 27, in 145 ℃ of reactions 3.5 hours, boil off moisture content and obtain solid phase prod.
Claims (3)
1. a humic acids resin fluid loss agent is characterized in that consisting of humic acids (HA) active intermediate, multiple polymers of water-soluble polypropylene nitrile ammonium salt and water-soluble carbon amide resins, and its each component weight percentage is:
HA active intermediate 15～70%
The multiple polymers 5～40% of water-soluble polypropylene nitrile ammonium salt
Water-soluble carbon amide resins 10～50%;
Described humic acid activity intermediate consists of humic acids content greater than 35% weathered coal, water and highly basic, and in order to preparation water mud fluid loss agent, its component content (weight ratio) is:
Weathered coal 1 water 2-5 highly basic 0.07-0.2;
The multiple polymers each component weight percent of described water-soluble polypropylene nitrile ammonium salt is:
Water 0.1-6
Hydrolyzed polyacrylonitrile ammonium salt 1
One or more mixtures 0.05-0.45 in polyacrylamide, sulfomethylation polyacrylamide, carboxymethyl cellulose, Natvosol, polyoxyethylene glycol, polyvinyl alcohol, polyoxyethylene phenol ether, the borax;
Described water-soluble carbon amide resins each component weight ratio is:
Water 0.1-1
Formaldehyde 0.5-2.5
Highly basic 0.005-0.03;
The complex compound of Fe, the Al of carbon neutral acid amides, methylol phosphinylidyne ammonium, carboxamide, Zn, Mn, Ti, Zr, Hf or one or more mixtures 1 in the uride
One or more mixtures 0.05-1 in S-WAT, sodium bisulfite, ammonium sulphite, the Sodium Metabisulfite.
2. a kind of humic acids resin fluid loss agent according to claim 1 is characterized in that described highly basic is a kind of or its mixture among KOH and the NaOH.
3. the preparation method of a kind of humic acids resin fluid loss agent according to claim 1 is characterized in that concrete steps are as follows:
(1) preparation of humic acids (HA) active intermediate
Be that feedstock production is when being applicable to NaCl≤4% fresh water less salt type mud system product with the weathered coal
A. by the weighing of described humic acids (HA) active intermediate component content;
B. add entry in weathered coal, highly basic obtained humic acids (HA) active intermediate in 0.5-3 hour in 30-150 ℃ of reaction;
(2) preparation of the multiple polymers of water-soluble polypropylene nitrile ammonium salt
A. by the multiple polymers component content weighing of described water-soluble polypropylene nitrile ammonium salt;
B. water is mixed with water Jie polyacrylonitrile ammonium salt with one or more mixtures in polyacrylamide, sulfomethylation polyacrylamide, carboxymethyl cellulose, Natvosol, polyoxyethylene glycol, polyvinyl alcohol, polyoxyethylene phenol ether, the borax, under 20～100 ℃ of temperature, react and got final product in 0.2～2 hour;
(3) preparation of water-soluble carbon amide resins
A. press the composition content weighing of described water-soluble carbon amide resins;
B. various components are mixed, under 50-150 ℃ of temperature, react and got final product in 0.5～4 hour;
(4) synthetic fluid loss agent
1. a. forms the product that (1), (2), (3) step make by described humic acids resin fluid loss agent
The content weighing;
B. the product that (1), (2), (3) step are made adds in the reactor simultaneously, at 100-160 ℃
After reaction in 1-6 hour, boil off moisture content under the temperature and obtain solid phase prod.
2. a. makes composition (2), (3) step by forming humic acids resin fluid loss agent component content
The component of product is by above-mentioned its component content weighing;
B. (2), (3) step being prepared required component adds in the intermediate that is made by (1) simultaneously
After reaction in 1-6 hour, boil off moisture content under the 100-160 ℃ of temperature and obtain solid phase prod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113858A CN1048999C (en) | 1994-11-01 | 1994-11-01 | Filtering-loss reducing agent of humic resin and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113858A CN1048999C (en) | 1994-11-01 | 1994-11-01 | Filtering-loss reducing agent of humic resin and its prepn |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99107926 Division CN1084781C (en) | 1999-06-03 | 1999-06-03 | Leonardite resin brine type filter loss reduction agent and method for prep. same |
| CN 99107925 Division CN1084780C (en) | 1999-06-03 | 1999-06-03 | Lignite resin type high temp. salt resistant filter loss reduction agent and method for prep. same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1122356A CN1122356A (en) | 1996-05-15 |
| CN1048999C true CN1048999C (en) | 2000-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113858A Expired - Fee Related CN1048999C (en) | 1994-11-01 | 1994-11-01 | Filtering-loss reducing agent of humic resin and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048999C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100338169C (en) * | 2005-12-22 | 2007-09-19 | 新疆三精德润科技有限公司 | Fluid loss additive for boring fluid |
| CN101230257B (en) * | 2007-12-28 | 2011-02-02 | 中国石油大学(华东) | Method for preparation of lignite resin drilling fluid loss additive |
| CN103849361A (en) * | 2014-02-13 | 2014-06-11 | 克拉玛依友联实业有限责任公司 | High-temperature resistant anti-collapse blocking agent and preparation method thereof |
| CN104479142B (en) * | 2014-12-04 | 2016-09-21 | 太原师范学院 | A kind of method that humic acids unstressed configuration processes and the application in prepared by anti-sloughing agent thereof |
| CN106608977B (en) * | 2015-10-27 | 2019-05-24 | 新疆真帝石油科技有限公司 | A kind of manufacturing method of sulfonated humic acid polymer and the application of sulfonated humic acid polymer |
| CN109777380A (en) * | 2017-11-13 | 2019-05-21 | 中石化石油工程技术服务有限公司 | Shale inhibition filtrate reducer for drilling fluid and preparation method thereof |
| CN111690385A (en) * | 2020-06-30 | 2020-09-22 | 乌海市盛世源石油科技有限公司 | Filtrate reducer lignite resin for drilling fluid and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106524A (en) * | 1985-08-31 | 1986-07-09 | 中国科学院化学研究所 | A kind of novel treating agent of drilling mud and preparation method who contains humic acids |
| EP0228497A1 (en) * | 1986-01-10 | 1987-07-15 | Vladimir Dr. Manojlovic | A process for water purification, and a filter for carrying out the process |
| CN1058983A (en) * | 1991-05-13 | 1992-02-26 | 西南石油学院 | A kind of preparation method of cement filter loss-reducing agent for oil well |
| CN1059925A (en) * | 1991-05-13 | 1992-04-01 | 西南石油学院 | A kind of composite cement filter loss-reducing agent for oil well |
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1994
- 1994-11-01 CN CN94113858A patent/CN1048999C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106524A (en) * | 1985-08-31 | 1986-07-09 | 中国科学院化学研究所 | A kind of novel treating agent of drilling mud and preparation method who contains humic acids |
| EP0228497A1 (en) * | 1986-01-10 | 1987-07-15 | Vladimir Dr. Manojlovic | A process for water purification, and a filter for carrying out the process |
| CN1058983A (en) * | 1991-05-13 | 1992-02-26 | 西南石油学院 | A kind of preparation method of cement filter loss-reducing agent for oil well |
| CN1059925A (en) * | 1991-05-13 | 1992-04-01 | 西南石油学院 | A kind of composite cement filter loss-reducing agent for oil well |
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| Publication number | Publication date |
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| CN1122356A (en) | 1996-05-15 |
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