發(fā)布時間：2018-07-22 20:54

【摘要】：在地下鹵水的開采過程中,隨著地下地質條件及其采提鹵過程中溫度和壓力的變化,鹵水中不同組分會發(fā)生不同程度的析晶、結垢現(xiàn)象,減小了管道的有效容積,增加了管道阻力,進而減少了產量,制約了鹵水的開采和可持續(xù)利用。針對鹵水開采過程中易出現(xiàn)的析晶、結垢現(xiàn)象,需要加入阻垢劑來抑制垢的產生,從而提高鹵水的開采量,降低能耗,確保采提鹵設備與構筑物的持續(xù)利用。在阻垢劑的研制過程中,要考慮到后續(xù)對環(huán)境的影響,所以要選擇無磷、無氮、易生物降解的單體制備。本文依托國家863計劃黃河三角洲深層鹵水高效開采關鍵技術,在查閱國內外相關文獻的基礎上,針對深層鹵水在采提輸過程中易發(fā)生不同程度的析鹽結垢問題,在分析采提鹵過程結垢機理的基礎上,研發(fā)了一種新型綠色阻垢劑,不僅對其抗溫性、抗鹽性進行了研究,還分析了其先進性、環(huán)境友好性以及阻垢機理,研究的主要內容和結果如下：(1)采用ICP-AES、離子選擇電極法、溫度壓力模擬法等分析手段,分別對不飽和、飽和鹵水在采提取過程中鹵水主要析鹽結垢元素的濃度變化及其主要析鹽結垢元素在各溫度、壓力下的飽和溶解度變化規(guī)律進行了系統(tǒng)研究,結果表明：①對于不飽和鹵水,鹵水主要析鹽結垢元素的濃度不隨提鹵深度的變化而變化；②對于飽和鹵水,主要析鹽結垢離子的濃度變化顯著,其中Ca2+最先析出,其次是Ba2+、Sr2+,同時伴隨著NaCl的析出。在從地下1500m提至500m的過程中,Sr2+的濃度變化最大；③常壓下飽和鹵水中四種主要析鹽結垢離子的飽和溶解度隨溫度的變化率與飽和溶解度隨提升高度的變化率基本一致。當溫度由120℃降至80℃時,Ca2+濃度的變化率最大,從80℃降至60℃時,Ba2+濃度的變化率最大,從60℃降至20℃時,Sr2+濃度的變化率最大；④60℃時,飽和鹵水中四種主要析鹽結垢離子的飽和溶解度隨壓力增加而增大,但變化率基本相同。因此,飽和鹵水在提輸過程中的溫度變化是影響析鹽結垢離子析出順序的主要因素。(2)鹽垢的形成過程可以表示為：鹵水→結垢元素飽和→結垢元素過飽和→形成晶核→NaCl共沉淀→晶體長大→鹽垢,而其主要成分為NaCl、CaSO4、 BaSO4、SrSO4。在采提過程中,不飽和鹵水中析鹽結垢現(xiàn)象較輕,飽和鹵水析鹽結垢現(xiàn)象嚴重。當溫度由120℃降至80℃時,形成的是以CaSO4為主BaSO4、 SrSO4為輔并吸附共沉淀NaCl的鹽垢；從80℃降至60℃時,形成的是以BaSO4為主CaSO4、SrSO4為輔并吸附共沉淀NaCl的鹽垢；從60℃降至20℃時,形成的是以SrSO4為主CaSO4、BaSO4為輔并吸附共沉淀NaCl的鹽垢。(3)結合上述析鹽結垢影響因素和形成過程的研究,詳細闡述了析鹽結垢機理,具體如下：隨著溫度、壓力等熱力學條件的改變,當溶液中的成垢離子濃度高于平衡濃度時,陰、陽離子相互作用形成離子對,離子對遇到管壁或其他雜質形成晶核,溶液中的成垢離子不斷向壁面擴散、結晶、長大,最終在管壁上形成結垢,由于吸附、共沉淀作用,NaCl晶體也隨之析出,形成混合鹽垢,析鹽與結垢之間存在著相互促進的關系。鹽垢的形成還會受到管道表面狀態(tài)、鹵水流速、微生物種類和數(shù)量等的影響。(4)通過研究聚環(huán)氧琥珀酸PESA、聚天冬氨酸PASP、木質素磺酸鈉、十二烷基硫酸鈉、脂肪醇聚氧乙烯醚AEO-9、壬基酚聚氧乙烯醚TX-10的阻垢抑垢性能,開發(fā)了以聚環(huán)氧琥珀酸和木質素磺酸鈉為主要成分的新型阻垢劑,并進行了性能測試,結果表明：該阻垢劑不含氮、磷,在聚環(huán)氧琥珀酸和木質素磺酸鈉復配比為3：2,投加量為35mg/L時,對鹵水中Na+、Ca2+、Ba2+、Sr2+的阻垢率分別達到了99.43%、99.45%、99.24%、90.85%,加權阻垢率99.15%;通過對比加入阻垢劑前后鹵水垢物、硫酸鈣、硫酸鋇、硫酸鍶、氯化鈉的掃描電鏡圖,得出新型復配阻垢劑對鹵水垢物的晶格畸變、螯合作用和電荷分散作用較強。其中對硫酸鈣的螯合作用和電荷分散作用較強,對硫酸鋇、硫酸鍶的晶格畸變、螯合作用較強,對氯化鈉的電荷分散作用較強。(5)新型阻垢劑在信發(fā)集團肥城勝利化工有限公司、東營東岳鹽業(yè)有限公司、山東默銳化工有限公司、壽光市國力化工有限公司分別進行了現(xiàn)場應用,應用結果表明：新型阻垢劑具有良好的阻垢性和一定的緩蝕作用,阻垢率可達到90%以上。與國內外適用于采提鹵過程中的阻垢劑相比,新型阻垢劑具有環(huán)境友好、不含磷氮、阻垢效果好、功能多等優(yōu)點。
[Abstract]:In the process of underground brine mining, with the change of temperature and pressure in the underground geological conditions and the process of extracting halogen, different fractions of the bittern occur in different degrees of crystallization and scaling, which reduces the effective volume of the pipeline, increases the pipe resistance, reduces the production and restricts the exploitation and sustainable utilization of the brine. In the process of water mining, the phenomenon of crystallization and scaling, which should be added to the scale inhibitor, should be added to inhibit the production of the scale, thus improving the production of the brine, reducing the energy consumption, and ensuring the continuous utilization of the equipment and structures of the halogen. In the process of developing the scale inhibitor, the effect of the follow-up on the environment should be taken into consideration, so the phosphorus free, nitrogen free and biodegradable materials should be selected. This paper relies on the key technology of high efficiency mining in the deep brine of the State 863 plan of the the Yellow River Delta. On the basis of consulting the relevant literature at home and abroad, the problem of salt precipitation and scaling is easy to occur in the process of extraction and transportation of deep brine, and a new green resistance is developed on the basis of the analysis of the scaling mechanism of the extraction and extraction of the brine. The scale agent not only studies its temperature resistance and salt resistance, but also analyzes its advanced, environmental friendly and scale inhibition mechanism. The main contents and results are as follows: (1) the main salt analysis of unsaturated and saturated brine during extraction and extraction by using ICP-AES, ion selective electrode method, temperature pressure simulation method and so on. The change of the concentration of the scaling elements and the variation of the saturated solubility of the main salt forming elements at various temperatures and pressures have been systematically studied. The results show that: (1) the concentration of the main salt precipitation and scaling elements in the halogen does not change with the change of the depth of the halogen. The concentration change is significant, in which Ca2+ is the first precipitation, followed by Ba2+, Sr2+, and the precipitation of NaCl. The concentration of Sr2+ has the greatest change in the process of extracting to 500m from the underground 1500m. (3) the change rate of the saturated solubility of the four main salt precipitation ions in the saturated brine under the atmospheric pressure and the change rate of the saturation solubility with the elevation of the saturation solubility. It is basically the same. When the temperature is reduced from 120 to 80, the change rate of Ca2+ concentration is the largest. The maximum change rate of Ba2+ concentration is the maximum from 80 C to 60 C. The maximum change rate of Sr2+ concentration is increased from 60 C to 20 C. At 60 C, the saturation solubility of four main salt precipitation ions in saturated brine increases with the pressure increase, but the change rate is basic. Therefore, the temperature change of the saturated brine during the extraction process is the main factor affecting the precipitation sequence of salt precipitation. (2) the formation process of salt scale can be expressed as: brine, scale element saturation, scaling element supersaturation, nucleation, NaCl co precipitation, crystal growth and salt scale, and its main components are NaCl, CaSO4, BaS. O4, SrSO4. in the process of extraction, the phenomenon of salt precipitation and scaling in unsaturated brine is light, and the scale phenomenon of salt precipitation in saturated brine is serious. When the temperature is reduced from 120 to 80, the formation of salt scale with CaSO4 as the main BaSO4, SrSO4 as auxiliary and adsorption coprecipitation NaCl; when from 80 to 60 C, BaSO4 is the main CaSO4, SrSO4 is supplemented and adsorbed together. The salt scale of NaCl was precipitated; from 60 to 20 C, the formation of salt scale with SrSO4 as the main CaSO4 and BaSO4 as the auxiliary and co precipitation of NaCl. (3) in combination with the influence factors and formation process of the above salt precipitation scaling, the mechanism of salt precipitation scaling was elaborated, as follows: with the change of the thermodynamic conditions, such as temperature, pressure and so on, when the solution was formed. When the concentration of the scale ion is higher than the equilibrium concentration, the anion and cation interact to form the ion pair. The ions form the nucleus of the tube wall or other impurities. The scale ions in the solution diffuse, crystallize, and grow up and eventually form a scale on the wall of the tube. Because of the adsorption and co precipitation, the NaCl crystal also precipitates, forming a mixed salt scale and salt evolution. There is a mutual promotion relationship with scaling. The formation of salt scale will also be influenced by the surface state of the pipe, the flow velocity of brine, the species and quantity of microorganism. (4) through the study of polyepoxide succinate PESA, polyaspartic acid PASP, sodium lignosulfonate, twelve alkyl sodium sulfate, fatty alcohol polyoxyethylene ether AEO-9, nonylphenol polyoxyethylene ether TX-1 0, a new scale inhibitor based on polyepoxysuccinic acid and sodium lignosulfonate was developed and tested. The results showed that the scale inhibitor did not contain nitrogen and phosphorus, and the scale inhibition rate of Na+, Ca2+, Ba2+, Sr2+ in brine when the ratio of polyepoxysuccinic acid to sodium lignosulfonate was 3:2 and the dosage was 35mg/L. The scale inhibition rate of 99.43%, 99.45%, 99.24%, 90.85%, and weighted scale inhibition rate is 99.15%, respectively. By comparing the scale of brine, calcium sulfate, barium sulfate, strontium sulphate, and sodium chloride, the lattice distortion of the new compound scale inhibitor on the scale of brine, the chelation and the charge dispersion are stronger. The lattice distortion of barium sulfate and strontium sulphate, strong chelation and the charge dispersion of sodium chloride are stronger for barium sulfate and strontium sulfate. (5) the new scale inhibitor is carried out in shinfa Feicheng Shengli Chemical Co., Ltd., Dongying Dongyue Salt Industry Co., Ltd., Shandong taco Chemical Co., Ltd., and Shouguang national strength Chemical Co., Ltd. The application results show that the new scale inhibitor has good scale inhibition and corrosion inhibition, and the scale inhibition rate can reach more than 90%. Compared with the scale inhibitor used in the process of extraction and extraction at home and abroad, the new scale inhibitor has the advantages of friendly environment, no phosphorus containing nitrogen, good scale inhibition effect and many functions.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ085.4

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