CN111676003B - Environment-friendly low-molecular-weight branched polyether ammonia shale intercalation inhibitor - Google Patents
Environment-friendly low-molecular-weight branched polyether ammonia shale intercalation inhibitor Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 59
- 229920000570 polyether Polymers 0.000 title claims abstract description 59
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 56
- 239000003112 inhibitor Substances 0.000 title claims abstract description 50
- 238000009830 intercalation Methods 0.000 title claims abstract description 23
- 230000002687 intercalation Effects 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000005580 one pot reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- -1 ester compound Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 claims description 12
- GTCAXTIRRLKXRU-UHFFFAOYSA-N carbamic acid methyl ester Natural products COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 claims description 2
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 claims description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000005553 drilling Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 description 13
- 230000005764 inhibitory process Effects 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Polyethers (AREA)
Abstract
一种环保型低分子量支化聚醚氨作为页岩插层抑制剂，属于油气田钻井技术领域，所述低分子量聚醚氨是以带有氨基和醚键的酯类化合物和含有烯键的醚类化合物为原料用一锅合成法或分步合成法合成。所述低分子量支化聚醚氨制成的页岩插层抑制剂是由低分子量支化聚醚氨与水混合配制而成，其中低分子量支化聚醚氨在页岩插层抑制剂中的质量比为0.5％‑3％。本发明提供的低分子量支化聚醚氨制成的页岩插层抑制剂具有良好的生物可降解性，安全无毒，且其抑制性能相比于同类插层抑制剂性能有明显提升，原料易得，价格便宜，提供的合成方法稳定可靠，适用于工业化生产。
An environmentally friendly low-molecular-weight branched polyether ammonia is used as a shale intercalation inhibitor, belonging to the technical field of oil and gas field drilling. Such compounds are synthesized by one-pot synthesis or step-by-step synthesis as raw materials. The shale intercalation inhibitor made of the low molecular weight branched polyether ammonia is prepared by mixing the low molecular weight branched polyether ammonia and water, wherein the low molecular weight branched polyether ammonia is in the shale intercalation inhibitor. The mass ratio of 0.5%-3%. The shale intercalation inhibitor made of the low molecular weight branched polyetheramine provided by the invention has good biodegradability, is safe and non-toxic, and its inhibitory performance is significantly improved compared with similar intercalation inhibitors. It is easy to obtain and cheap, and the provided synthetic method is stable and reliable, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of oil and gas field drilling, in particular to a low-molecular-weight branched polyether ammonia shale intercalation inhibitor.
Background
Borehole wall instability has always been a worldwide problem to be overcome during drilling. It often results in complex accidents such as borehole wall collapse, hole shrinkage, stuck drill, etc., increasing drilling time and drilling cost. According to statistical data, 75% of the borehole wall instability problems mainly occur in shale formations, particularly water-sensitive formations, the shale formations have high clay mineral content, the horizontal sections of shale gas horizontal wells are long, the drilling fluid is in contact with the formations for a long time, the shale is more seriously hydrated, and the borehole wall instability is more prominent. Although the oil-based drilling fluid has the advantages of high temperature resistance, salt and calcium corrosion resistance, contribution to well wall stability, good lubricity, small damage degree to an oil-gas layer and the like, the preparation cost of the oil-based drilling fluid is much higher than that of the water-based drilling fluid, the oil-based drilling fluid often causes serious influence on the ecological environment nearby a well site when in use, the mechanical drilling speed is generally lower than that of the water-based drilling fluid, and the popularization and the application of the oil-based drilling fluid are greatly limited by the defects.
With the gradual improvement of the environmental protection requirement in recent years, the development of water-based drilling fluid which has the same effect as oil-based drilling fluid and meets the environmental protection requirement to replace the oil-based drilling fluid is a trend of the current drilling fluid technology development. In order to overcome the defects of the existing inhibitor, researchers have conducted a great deal of experimental research on the inhibitor, but the variety really accepted by the market is not many, and particularly, the water-based drilling fluid which is suitable for high temperature and high density and meets the environmental protection requirement is still to be developed. In recent years, ether substances have attracted attention because of their advantages such as no biological toxicity, safety, and degradability.
The polyamine inhibitors studied and applied at present are mostly linear structures, and for the linear polyamine inhibitors, the linear polyamine inhibitors usually have irregular linear configurations after being dissolved in water, and when the linear polyamine inhibitors are used in a shale gas drilling process, winding and coating on clay are uneven, so that repeated adsorption or no adsorption is easily caused. Meanwhile, the acting groups are generally arranged at two ends of a molecular chain, so that one molecular chain generally only contains two acting groups, the acting effect of the linear polyether ammonia inhibitor is limited in this case, and the polyamine compound with high molecular weight is difficult to enter between clay layers, so that the inhibiting performance of the polyamine is limited.
Disclosure of Invention
Aiming at the defects of the existing shale intercalation inhibitor, the invention provides the shale intercalation inhibitor prepared from the environment-friendly branched polyether ammonia in view of the problems, the inhibitor responds to the environment-friendly requirement, the inhibition performance is obviously improved compared with similar products, the drilling requirements of various complex well conditions can be completely met, the synthesis process is simple and environment-friendly, the yield is higher, the production cost is low, and the shale intercalation inhibitor is suitable for industrial production.
In order to achieve the purpose, the technical scheme of the invention is as follows: the shale intercalation inhibitor is prepared by mixing low-molecular-weight branched polyether ammonia and water, wherein the mass ratio of the low-molecular-weight branched polyether ammonia is 0.5-3%, the low-molecular-weight branched polyether ammonia is synthesized by taking ester compounds with amino groups and ether bonds and ether compounds containing olefinic bonds as raw materials through a one-pot synthesis method or a distributed synthesis method.
The one-pot synthesis method comprises the following operation steps: respectively dissolving 0.1mol of ester compound with amino and ether bond (wherein the number of the amino groups is m) and 0.1m mol of ether compound containing olefinic bond in 80-100ml of equivalent solvent, and dropwise adding the ether compound solution containing olefinic bond into the ester compound solution with amino and ether bond under stirring at 25-35 deg.C under nitrogen atmosphere. After titration is finished, raising the temperature to 65-85 ℃, carrying out reflux reaction for 4-10h, and after the reaction is finished, carrying out rotary evaporation to obtain the G3 low-molecular-weight branched polyether ammonia.
The step-by-step synthesis method comprises the following operation steps:
s1, respectively dissolving 0.1mol of ester compound with amino and ether bond and 0.1mol of ether compound with olefinic bond in 80-100ml of equivalent solvent, and dropwise adding the ether compound solution with olefinic bond into the ester compound solution with amino and ether bond under the condition of stirring at 25-35 ℃ in nitrogen atmosphere. After titration is finished, raising the temperature to 65-85 ℃, carrying out reflux reaction for 4-10h, and after the reaction is finished, carrying out rotary evaporation to obtain the G1 low-molecular-weight branched polyether ammonia.
S2, respectively dissolving the G1 low molecular weight branched polyether ammonia obtained in S1 and 0.1mol of ether compound containing olefinic bond in 80-100ml of equivalent solvent, and dropwise adding the ether compound solution containing olefinic bond into the ester compound solution containing amino and ether bond under the condition of stirring at 25-35 ℃ in nitrogen atmosphere. After titration is finished, raising the temperature to 65-85 ℃, carrying out reflux reaction for 4-10h, and after the reaction is finished, carrying out rotary evaporation to obtain the G2 low-molecular-weight branched polyether ammonia.
S3, reacting the G2 low molecular weight branched polyether ammonia obtained in the S2 according to the step S2, wherein the maximum reaction step number of the reaction steps is m of hydrogen atoms of amino groups contained in ester compounds with amino groups and ether bonds, and obtaining the corresponding G1-Gm low molecular weight branched polyether ammonia after the reaction of the steps is finished.
The ester compound having an amino group and an ether bond is N- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- (2-aminoethoxy) ethyl ] ethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -1-methylethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] propyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -2-methylpropyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methylethyl ethoxy carbamate, 5,8, 11-trioxo-2-azadecanoic acid-1, 3-amino-1, 1-dimethylethyl ester, 5,8,11, 14-tetraoxy-2-azahexadecanoic acid-16-amino-1, 1-dimethylethyl ester, 5,8,11,14, 17-pentoxy-2-azaazelaic acid-19-nitrogen-1, 1-dimethylethyl ester, and an alkene compound containing an ether bond is one of vinyl n-butyl ether, vinyl isobutyl ether, 2-ethylhexyl vinyl ether, 2-methoxyethyl vinyl ether and 2- [ (2-methoxy) ethoxy ] ethyl ether.
The titration time of the dripping step is controlled to be 25-35 min.
The rotary evaporation temperature is 65 ℃, and the absolute vacuum degree is less than 3000 Pa.
The invention has the following beneficial effects:
1. the product designed by the invention responds to the requirement of environmental protection, has the advantages of no biological toxicity, safety and easy degradation, and belongs to an environment-friendly inhibitor;
2. the synthesis method has stable and reliable technology, high yield and low price of raw materials required by the synthesized product, and is suitable for industrial production;
3. the shale inhibitor provided by the invention is a low molecular weight branched polyetheramine shale intercalation inhibitor, has stable performance and strong adaptability, has obviously improved inhibition performance compared with similar products, and can meet the drilling requirements of various complex well conditions.
Drawings
FIG. 1 is a graph showing the distribution of the molecular weight of G3 low molecular weight branched polyether ammonia in example 1;
FIG. 2 is a graph showing the distribution of the molecular weight of G1 low molecular weight branched polyether ammonia in example 2;
FIG. 3 is a graph showing the distribution of the molecular weight of G2 low molecular weight branched polyether ammonia in example 2;
FIG. 4 is a graph showing the distribution of the molecular weight of G3 low molecular weight branched polyether amine in example 2;
FIG. 5 is a graph showing the distribution of the molecular weight of G1 low molecular weight branched polyether amine in example 3;
FIG. 6 is a graph showing the distribution of the molecular weight of G2 low molecular weight branched polyether amine in example 3;
FIG. 7 is a graph showing the distribution of the molecular weight of G3 low molecular weight branched polyether ammonia in example 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the preparation method of the low molecular weight branched polyether ammonia by using carbamic acid N- [2- (2-aminoethoxy) ethyl ] methyl ester and vinyl isobutyl ether as raw materials and adopting a one-pot method comprises the following specific operation steps:
0.1mol of N- [2- (2-aminoethoxy) ethyl ] methyl carbamate and 0.3mol of vinyl isobutyl ether are weighed out accurately and dissolved in 100ml of anhydrous methanol. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G3 low-molecular-weight branched polyether ammonia. The molecular structural formula is as follows:
example 2:
the branched polyether ammonia with low molecular weight is prepared by a fractional synthesis method by taking carbamic acid N- [2- (2-aminoethoxy) ethyl ] methyl ester and vinyl isobutyl ether as raw materials, and the specific operation steps are as follows:
0.1mol of N- [2- (2-aminoethoxy) ethyl ] methyl carbamate and 0.1mol of vinyl isobutyl ether are weighed out accurately and dissolved in 100ml of anhydrous methanol. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G1 low-molecular-weight branched polyether ammonia. The molecular structural formula is
0.1mol of G1 low molecular weight branched polyetheramine and 0.1mol of vinyl isobutyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol, respectively. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the completion of the dropwise addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G2 low-molecular-weight branched polyether ammonia. The molecular structural formula is
0.1mol of G2 low molecular weight branched polyetheramine and 0.1mol of vinyl isobutyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol, respectively. N- [2- (2-aminoethoxy) ethyl ] methyl carbamate was placed in a three-necked flask, and vinyl isobutyl ether was placed in a separatory funnel and added dropwise into the three-necked flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G3 low-molecular-weight branched polyether ammonia. The molecular structural formula is
Example 3:
the low molecular weight branched polyether ammonia is prepared by taking carbamic acid N- [2- [2- (2-aminoethoxy) ethoxy ] ethyl ] methyl ester and vinyl N-butyl ether as raw materials and adopting a stepwise synthesis method, and the specific operation steps are as follows:
0.1mol of N- [2- [2- (2-aminoethoxy) ethoxy ] ethyl ] methyl carbamate and 0.1mol of vinyl N-butyl ether are weighed out accurately and dissolved in 100ml of anhydrous methanol. N- [2- [2- (2-aminoethoxy) ethoxy ] ethyl ] methyl carbamate was placed in a three-neck flask, and vinyl N-butyl ether was placed in a separatory funnel and added dropwise to the three-neck flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G1 low-molecular-weight branched polyether ammonia.
The molecular structural formula is
0.1mol of G1 low molecular weight branched polyetheramine and 0.1mol of vinyl n-butyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol, respectively. G1 low molecular weight branched polyether ammonia was placed in a three-neck flask, and vinyl n-butyl ether was placed in a separatory funnel and added dropwise into the three-neck flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G2 low-molecular-weight branched polyether ammonia. The molecular structural formula is
0.1mol of G2 low molecular weight branched polyetheramine and 0.1mol of vinyl n-butyl ether were weighed out accurately and dissolved in 100ml of anhydrous methanol respectively. G2 low molecular weight branched polyether ammonia was placed in a three-neck flask, and vinyl n-butyl ether was placed in a separatory funnel and added dropwise into the three-neck flask at a temperature of 30 ℃ under a nitrogen atmosphere with stirring. After the addition, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After the reaction is finished, the product is subjected to rotary evaporation at the temperature of 65 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G3 low-molecular-weight branched polyether ammonia. The molecular structural formula is
1. Molecular weight measurement
The hyperbranched polyguanylic acid contained in the examples was subjected to a molecular weight test using TOF-LC/MS, and the test results are shown in FIGS. 1 and 2. According to the results of polymer mass spectrum tests, G3 low molecular weight branched polyether ammonia obtained in example 1 shows peaks at positions 366.396, 367.241, 368.024 and 369.712, respectively, which are consistent with theoretical values, and G2 low molecular weight branched polyether ammonia obtained in example 2 shows peaks at positions 307.326, 308.021, 309.413 and 310.502, respectively, which are consistent with theoretical values. Thus demonstrating the success of low molecular weight branched polyether ammonia synthesis.
2. Linear expansion rate test
The low molecular weight branched polyether ammonia obtained in example 1-2 and clean water were prepared in a ratio (the low molecular weight branched polyether ammonia mass ratio was 1%, 2%, 3%) into shale inhibitors and conventional shale inhibitors (conventional polyamine inhibitors and hexamethylenediamine inhibitors were selected) for comparative experiments, and clean water was used as a reference. The inhibition performance prepared in the above examples is evaluated by adopting a linear expansion ratio, and the specific operation steps refer to the petroleum and natural gas industry standard SY/T6335-1997 evaluation method of shale inhibitors for drilling fluids. The lower the linear expansion ratio, the better the inhibition performance of the inhibitor. The results of the experiments are shown in the following table.
TABLE 1 Effect of different intercalation inhibitors on Linear expansion Rate
TABLE 2 Effect of intercalation inhibitor addition on Linear expansion Rate
The results of the influence of different intercalation inhibitors on the linear expansion rate in table 1 show that when ethylenediamine, polyamine and the low molecular weight branched polyether ammonia obtained in different examples are in the same proportion, the inhibition performance of the low molecular weight branched polyether ammonia is obviously higher than that of the conventional shale inhibitors such as hexamethylenediamine and polyamine. The inhibition effect of the low molecular weight branched polyether ammonia shale inhibitor is obviously higher than that of the conventional shale inhibitor. The influence of the inhibitor content on the linear expansion rate shows that the linear expansion rate is reduced along with the increase of the inhibitor addition amount, the inhibition performance is better, and when the inhibitor addition amount reaches 4%, the inhibition effect reaches a peak value.
3. Environmental protection test
The low molecular weight branched polyether ammonia serving as the shale intercalation inhibitor has the advantages of excellent inhibition performance, simple production process and easy biodegradation. The international Organization for Economic Cooperation and Development (OECD) issued a series of standards on biodegradability of chemicals, which have become an important basis for environmental hazard assessment and risk assessment of chemicals, wherein the OECD301 series of standards specifies 6 chemical rapid biodegradation test methods, according to which test methods can be considered as biodegradable substances. According to the test standard of the sealed bottle method (301D), when the biodegradation rate (BOD/COD) of the chemical is 28 days, the biodegradation rate BOD/COD is not less than 60%, and it can be considered that the chemical is easily biodegraded.
The biodegradability (BOD5/CODcr) is used herein to represent the biodegradability, BOD5 (reference standard HJ/T505-2009) is determined by inoculation and dilution methods, CODcr (reference standard YJ/T377-2007) is determined by potassium dichromate method, BOD5/CODcr is respectively measured for G3 low molecular weight branched polyether ammonia in example 1, G1 low molecular weight branched polyether ammonia in example 2, G2 in example 2, G3 in example 2, example 3G1, example 3G2, and example 3G3, and the final results are respectively 61.2%, 64.8%, 63.2%, 61.4%, 64.3%, 62.7%, 60.9%, thus the product can reach the OECD environmental protection standard and is easily degraded compared with hexamethylenediamine, which is a commonly used inhibitor in the art, and the BOD of the product is easily degraded5The ratio of/CODcr is 1%, which is much lower than the normal index, indicating poor biodegradability. The product is an environment-friendly shale inhibitor, and compared with the conventional inhibitor, the environment-friendly performance of the product is obviously improved.
In conclusion, the preparation method of the low molecular weight branched polyether ammonia provided by the invention has the advantages of stable and reliable technology and high yield, and is suitable for industrial production; the synthesized low molecular weight branched polyether ammonia product is non-toxic and harmless, has good water solubility, and the inhibition performance of the prepared shale intercalation inhibitor is obviously improved compared with similar products, thereby meeting the drilling requirements of various complex well conditions and effectively reducing the occurrence probability of unstable well wall caused by shale hydration dispersion.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The environment-friendly low-molecular-weight branched polyether ammonia shale intercalation inhibitor is characterized in that the shale intercalation inhibitor is prepared by mixing low-molecular-weight branched polyether ammonia and water, wherein the mass ratio of the low-molecular-weight branched polyether ammonia is 0.5-3%, and the low-molecular-weight polyether ammonia is synthesized by taking an ester compound with amino and ether bonds and an ether compound with olefinic bonds as raw materials by a one-pot synthesis method or a step synthesis method;
the ester compound having an amino group and an ether bond is N- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- (2-aminoethoxy) ethyl ] ethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -1-methylethyl carbamate, N- [2- (2-aminoethoxy) ethyl ] propyl carbamate, N- [2- (2-aminoethoxy) ethyl ] -2-methylpropyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methyl carbamate, N- [2- [2- (2-aminoethoxy) ethyl ] methylethyl ethoxy carbamate, 5,8, 11-trioxa-2-aza decanoic acid-1, 3-amino-1, 1-dimethyl ethyl ester, 5,8,11, 14-tetraoxy-2-aza hexadecanoic acid-16-amino-1, 1-dimethyl ethyl ester, 5,8,11,14, 17-pentoxy-2 aza azelaic acid-19-nitrogen radical-1, 1-dimethyl ethyl ester.
The alkene compound containing ether bond is one of vinyl n-butyl ether, vinyl isobutyl ether, 2-ethylhexyl vinyl ether and 2-methoxyethyl vinyl ether.
2. The inhibitor according to claim 1, wherein the one-pot synthesis comprises the following steps:
respectively dissolving 0.1mol of ester compound with amino and ether bond and 0.1m mol of ether compound with olefin bond in 80-100ml of equivalent solvent, wherein m is the number of amino groups contained in the ester compound with amino and ether bond, dripping the ether compound solution with olefin bond into the ester compound solution with amino and ether bond under the conditions of 25-35 ℃ temperature, nitrogen atmosphere and stirring, completing titration, heating to 65-85 ℃, carrying out reflux reaction for 4-10h, and carrying out rotary evaporation after the reaction is completed to obtain the Gm low molecular weight branched polyether ammonia.
3. The inhibitor according to claim 1, characterized in that the distributed synthesis method comprises the following steps:
s1, respectively dissolving 0.1mol of ester compound with amino and ether bond and 0.1mol of ether compound with olefinic bond in 80-100ml of equivalent solvent, dropwise adding the ether compound solution with olefinic bond into the ester compound solution with amino and ether bond under the conditions of 25-35 ℃ and nitrogen stirring, raising the temperature to 65-85 ℃ after titration, carrying out reflux reaction for 4-10h, and carrying out rotary evaporation after the reaction is finished to obtain G1 low-molecular-weight branched polyether ammonia;
s2, taking the product obtained in the previous step and the ether compound containing the olefinic bond with the same molar weight as the product, repeating the step S1 m times, wherein m is the number of amino groups of the ester compound with amino and ether bonds used in the step S1, and the product obtained in each step is G1-Gm low molecular weight branched polyetheramine.
4. The shale intercalation inhibitor made of low molecular weight branched polyether ammonia according to claim 2 or 3, wherein the solvent is one of absolute methanol, absolute ethanol, tetrahydrofuran, DMSO, DMF.
5. The shale intercalation inhibitor made of environment-friendly low molecular weight branched polyether ammonia as claimed in claim 2 or 3, wherein the dropping time is controlled within 25-35 min.
6. The shale intercalation inhibitor made of environment-friendly low-molecular-weight branched polyether ammonia as claimed in claim 2 or 3, wherein the rotary evaporation temperature is 65 ℃ and the absolute vacuum degree is less than 3000 Pa.
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