技术领域：Technical field:
本发明属于化学、化工、石油等行业高浓度无机盐溶液的结晶抑制领域，尤其是涉及到一种盐结晶抑制剂的简便合成及其使用。The invention belongs to the field of crystallization inhibition of high-concentration inorganic salt solutions in chemical, chemical, petroleum and other industries, and in particular relates to the simple synthesis and use of a salt crystallization inhibitor.
背景技术：Background technique:
在石油行业，钻井泥浆、采油、卤水的开采和输送高浓度的盐溶液会堵塞管道，影响正常生产，如我国川西卤水蕴藏在4000m以下的海相沉积层，其含有丰富的钾资源和高浓度的氯化钠溶液，在开采过程中由于温差过大，至井口时时常结晶堵死输送管道，导致丰富资源被迫停止开采。一些化工行业在无机盐产品的合成、转化、浓缩过程中，盐结晶也会堵塞设备或卡泵，导致设备无法运转，如我国的青海、新疆等地钾肥生产基地时常在冬天出现卡泵现象。为有效解决这些问题目前普遍采用的方式是热溶解，这不仅浪费能源，操作上也很不方便，因为温度的波动存在高浓度的盐溶液就时刻有结晶的可能，一旦积攒过多就会造成停产。对高浓度盐结晶抑制剂的研究也取得了一些进展，如浙江大学发明了一种使用结晶抑制剂的石材和石质文物的脱盐方法(CN101921135 A)，对氯化物碱金属盐类使用亚铁氰化物作结晶抑制剂，对碱金属的硫酸盐类使用有机磷酸类结晶抑制剂，浓度均在0.02-0.5mol/L之间，此类结晶抑制剂使用浓度相对较高，不适合规模化的应用。英国石油勘探运作有限公司发明了抑制产油井中结垢的方法(PCT/GB2003/002100)，其使用的结垢抑制剂有α，β-烯属不饱和羧酸、有机膦酸盐和聚膦酸盐、苯乙烯磺酸的均聚物、乙烯磺酸和苯乙烯磺酸的共聚物、聚乙烯醇等，此抑制剂合成步骤较多，成本偏高，未得到较好应用。原江汉石油学院发明了一种抑制氯化钠的结晶抑制剂(江汉石油学院学报，1988，1)，主要成分为铁、钠、钾的络合物，其中亚铁氰化物就是其中的一种。所有这些，其抑制原理都是增加盐在水中的溶解度，并使其晶体由立方体变为树枝状，使盐晶体对钢铁、玻璃表面的粘附力降低，不粘附在表面。目前我们发明了一种低浓度的高效盐结晶抑制剂，能够在较大的温度范围内使其盐饱和溶液不结晶，可以规模化应用。In the petroleum industry, drilling mud, oil production, brine exploitation and transportation of high-concentration salt solution will block pipelines and affect normal production. During the mining process, due to the large temperature difference, the sodium chloride solution often crystallizes and blocks the transportation pipeline when it reaches the wellhead, resulting in the cessation of mining of rich resources. In the process of synthesis, conversion and concentration of inorganic salt products in some chemical industries, salt crystallization will also block equipment or pumps, resulting in equipment failure. For example, potassium fertilizer production bases in Qinghai, Xinjiang and other places in my country often have pumps stuck in winter. In order to effectively solve these problems, the currently commonly used method is thermal dissolution, which not only wastes energy, but also is very inconvenient in operation, because there is a possibility of crystallization in the presence of high-concentration salt solution in temperature fluctuations, and once it accumulates too much, it will cause discontinued. Some progress has also been made in the research on high-concentration salt crystallization inhibitors, such as Zhejiang University invented a method for desalination of stone and stone cultural relics using crystallization inhibitors (CN101921135 A), using ferrous chloride for alkali metal salts Cyanide is used as a crystallization inhibitor, and organic phosphoric acid crystallization inhibitors are used for alkali metal sulfates, and the concentration is between 0.02-0.5mol/L. The concentration of such crystallization inhibitors is relatively high and is not suitable for large-scale production. application. British Petroleum Exploration and Operation Co., Ltd. invented a method for inhibiting scaling in oil production wells (PCT/GB2003/002100), and the scaling inhibitors used include α, β-ethylenically unsaturated carboxylic acid, organic phosphonate and polyphosphine Acid salts, homopolymers of styrene sulfonic acid, copolymers of ethylene sulfonic acid and styrene sulfonic acid, polyvinyl alcohol, etc. This inhibitor has many synthesis steps and high cost, so it has not been well used. The former Jianghan Institute of Petroleum invented a crystallization inhibitor to inhibit sodium chloride (Journal of Jianghan Institute of Petroleum, 1988, 1), the main component is a complex of iron, sodium, and potassium, and ferrocyanide is one of them . All of these, the inhibition principle is to increase the solubility of salt in water, and make the crystal change from cube to dendrite, so that the adhesion of salt crystal to steel and glass surface is reduced, and it does not adhere to the surface. At present, we have invented a low-concentration and high-efficiency salt crystallization inhibitor, which can make the salt-saturated solution not crystallize in a large temperature range, and can be applied on a large scale.
发明内容：Invention content:
本发明的目的在于为解决高浓度盐结晶堵塞管道、设备的问题而提供一种合成简便、配方简单、成本低廉、使用效果明显的简便合成盐结晶抑制剂，以适合石油、无机化工行业规模化使用。The purpose of the present invention is to provide a simple synthetic salt crystallization inhibitor with simple synthesis, simple formula, low cost and obvious effect in order to solve the problem of high-concentration salt crystallization blocking pipelines and equipment, so as to be suitable for large-scale production in petroleum and inorganic chemical industries use.
本发明专利所采用的技术方案是：以乙二醇和氨三乙酸为原料通过加热反应，以粗孔硅胶为吸水剂制作主抑制剂氨三乙酰胺，再与表面活性剂混合均匀即可制成总结晶抑制剂，使用时按比例加入盐溶液中即可抑制饱和盐溶液结晶。其合成工艺流程如下：The technical scheme adopted in the patent of the present invention is: use ethylene glycol and nitrilotriacetic acid as raw materials through heating reaction, use coarse-pore silica gel as water-absorbing agent to make main inhibitor nitrilotriacetamide, and then mix it with surfactant evenly to make it The total crystallization inhibitor, when used, can be added to the salt solution in proportion to inhibit the crystallization of the saturated salt solution. Its synthesis process is as follows:
（1）主结晶抑制剂的合成：(1) Synthesis of the main crystallization inhibitor:
按摩尔比乙二醇：氨三乙酸=6~7：1加入反应容器中，再按质量比氨三乙酸：粗孔硅胶=1：1～2将粗孔硅胶小心加入反应容器中，加热至200℃并恒温3小时以上反应完成，冷却，倒出粗孔硅胶，继续冷却至90℃时通入干燥的氨气直至生成的混合物冷却至35℃左右，所得浆状物过滤并用甲醇洗涤干净得到无色氨三乙酰胺，即为主抑制剂；According to the molar ratio of ethylene glycol: nitrilotriacetic acid = 6 ~ 7: 1, add to the reaction vessel, and then according to the mass ratio of nitrilotriacetic acid: coarse pore silica gel = 1: 1 ~ 2, carefully add the coarse pore silica gel to the reaction vessel, and heat to 200°C and constant temperature for more than 3 hours to complete the reaction, cool down, pour out the coarse-porous silica gel, continue to cool to 90°C, and pass dry ammonia gas until the resulting mixture cools to about 35°C, filter the resulting slurry and wash it with methanol to obtain Colorless aminotriacetamide, the main inhibitor;
（2）总结晶抑制剂的制作：(2) Preparation of total crystallization inhibitor:
按质量比氨三乙酰胺：表面活性剂=100：1~1.2混合均匀即成总结晶抑制剂。所述表面活性剂为乙二胺四乙酸四钠。According to the mass ratio of ammonia triacetamide:surfactant=100:1~1.2, mix evenly to form the total crystallization inhibitor. The surfactant is tetrasodium edetate.
使用时按盐溶液量加入总结晶抑制剂，保证总结晶抑制剂在盐溶液中占千分之一以上即可。When in use, add the total crystallization inhibitor according to the amount of the salt solution to ensure that the total crystallization inhibitor accounts for more than one thousandth of the salt solution.
本发明的有益效果在于：无需惰性气体保护，加入粗孔硅胶作为吸水剂可以及时吸收反应生成的水，有利于反应正向进行和确保反应温度不下降，表面活性剂保证器壁光滑。具有合成简便、配方简单、成本低廉、使用效果明显等优点，可广泛应用于化学、化工、石油等行业高浓度无机盐溶液的结晶抑制领域。The beneficial effect of the present invention is that: no inert gas protection is needed, and the addition of coarse-pore silica gel as a water-absorbing agent can absorb the water generated by the reaction in time, which is beneficial to the forward progress of the reaction and ensures that the reaction temperature does not drop, and the surface active agent ensures smooth walls. It has the advantages of simple synthesis, simple formula, low cost, obvious application effect, etc., and can be widely used in the field of crystallization inhibition of high-concentration inorganic salt solutions in industries such as chemistry, chemical industry, and petroleum.
具体实施方式：detailed description:
盐结晶抑制剂的简便合成工艺以乙二醇和氨三乙酸为原料通过加热反应，以粗孔硅胶为吸水剂制作主抑制剂氨三乙酰胺，再与表面活性剂混合均匀即可制成总结晶抑制剂，使用时按比例加入盐溶液中即可抑制饱和盐溶液结晶。其合成工艺流程如下：The simple synthesis process of salt crystallization inhibitor uses ethylene glycol and nitrilotriacetic acid as raw materials through heating reaction, and uses coarse-porous silica gel as water-absorbing agent to make the main inhibitor nitrilotriacetamide, and then mixes it with surfactant to make the total crystal Inhibitor, when used in proportion to add to the salt solution can inhibit the crystallization of saturated salt solution. Its synthesis process is as follows:
（1）主结晶抑制剂的合成：(1) Synthesis of the main crystallization inhibitor:
按摩尔比乙二醇：氨三乙酸=6~7：1加入反应容器中，再按质量比氨三乙酸：粗孔硅胶=1：1～2将粗孔硅胶小心加入反应容器中，加热至200℃并恒温3小时以上反应完成，冷却，倒出粗孔硅胶，继续冷却至90℃时通入干燥的氨气直至生成的混合物冷却至35℃左右，所得浆状物过滤并用甲醇洗涤干净得到无色氨三乙酰胺，即为主抑制剂；According to the molar ratio of ethylene glycol: nitrilotriacetic acid = 6 ~ 7: 1, add to the reaction vessel, and then according to the mass ratio of nitrilotriacetic acid: coarse pore silica gel = 1: 1 ~ 2, carefully add the coarse pore silica gel to the reaction vessel, and heat to 200°C and constant temperature for more than 3 hours to complete the reaction, cool down, pour out the coarse-porous silica gel, continue to cool to 90°C, and pass dry ammonia gas until the resulting mixture cools to about 35°C, filter the resulting slurry and wash it with methanol to obtain Colorless aminotriacetamide, the main inhibitor;
（2）总结晶抑制剂的制作：(2) Preparation of total crystallization inhibitor:
按质量比氨三乙酰胺：表面活性剂=100：1~1.2混合均匀即成总结晶抑制剂。According to the mass ratio of ammonia triacetamide:surfactant=100:1~1.2, mix evenly to form the total crystallization inhibitor.
使用时按盐溶液量加入总结晶抑制剂，保证总结晶抑制剂在盐溶液中占千分之一以上即可。When in use, add the total crystallization inhibitor according to the amount of the salt solution to ensure that the total crystallization inhibitor accounts for more than one thousandth of the salt solution.
下面通过实施例对本发明作进一步的说明。Below by embodiment the present invention will be further described.
实施例1：Example 1:
取3500g乙二醇、1500g氨三乙酸一并加入5L的圆底反应釜，再缓缓加入粗孔硅胶1700g，加热反应釜至200℃，恒温4小时，冷却至110℃，倾倒出粗孔硅胶，待反应混合物温度降到90℃时持续通入干燥的氨气直至温度降至35℃时停止通入氨气，所得浆状物过滤，甲醇洗涤，干燥，得到产品氨三乙酰胺1378g。称取氨三乙酰胺1000g，乙二胺四乙酸四钠10g，混匀得总抑制剂，备用。Take 3500g of ethylene glycol and 1500g of nitrilotriacetic acid and add them to a 5L round-bottomed reactor, then slowly add 1700g of coarse-pored silica gel, heat the reactor to 200°C, keep the temperature for 4 hours, cool to 110°C, and pour out the coarse-pored silica gel , when the temperature of the reaction mixture drops to 90° C., dry ammonia gas is continuously fed until the temperature drops to 35° C., and the ammonia gas is stopped. The resulting slurry is filtered, washed with methanol, and dried to obtain 1378 g of the product ammonia triacetamide. Weigh 1000 g of nitrilotriacetamide and 10 g of tetrasodium ethylenediaminetetraacetate, mix well to obtain the total inhibitor, and set aside.
及时量取四川平落坝出井卤水500L，出井口卤水温度102℃，离子组成为：Na+：93.386g/L；Cl-：215.35g/L；Ca2+：3.177g/L；Mg2+：3.726g/L；K+：50.928g/L。自然冷却至35℃，析盐量19.8kg(湿重)。同样条件下在102℃加入总抑制剂700g，迅速溶解后自然降至室温，未发现明显结晶物。Timely measure 500L of brine from Pingluoba, Sichuan. The temperature of the brine at the wellhead is 102°C. The ion composition is: Na+ : 93.386g/L; Cl- : 215.35g/L; Ca2+ : 3.177g/L; Mg2+ : 3.726g/L; K+ : 50.928g/L. Naturally cooled to 35°C, the amount of salt precipitation was 19.8kg (wet weight). Under the same conditions, 700 g of total inhibitors were added at 102°C, and after rapidly dissolving, it cooled down to room temperature naturally, and no obvious crystals were found.
实施例2：Example 2:
2500g乙二醇，1100g氨三乙酸一并加入5L的圆底反应釜，再缓缓加入粗孔硅胶2000g，加热反应釜至200℃，恒温4小时，冷却至110℃，倾倒出粗孔硅胶，待反应混合物温度降到90℃时持续通入干燥的氨气直至温度降至35℃时停止通入氨气，所得浆状物过滤，甲醇洗涤，干燥，得到产品氨三乙酰胺1008g。Add 2500g of ethylene glycol and 1100g of nitrilotriacetic acid into a 5L round-bottomed reactor, then slowly add 2000g of coarse-pored silica gel, heat the reactor to 200°C, keep the temperature constant for 4 hours, cool to 110°C, pour out the coarse-pored silica gel, When the temperature of the reaction mixture drops to 90° C., continue to feed dry ammonia until the temperature drops to 35° C. and stop feeding ammonia. The resulting slurry is filtered, washed with methanol, and dried to obtain 1008 g of the product ammoniatriacetamide.
称取氨三乙酰胺1000g，乙二胺四乙酸四钠10g，混匀得总抑制剂，备用。Weigh 1000 g of nitrilotriacetamide and 10 g of tetrasodium ethylenediaminetetraacetate, mix well to obtain the total inhibitor, and set aside.
及时量取四川平落坝出井卤水500L，出井口卤水温度102℃，离子组成为：Timely measure 500L of well-exited brine from Pingluoba, Sichuan. The temperature of the well-exited brine is 102°C. The ion composition is:
Na+：93.386g/L；Cl-：215.35g/L；Ca2+：3.177g/L；Mg2+：3.726g/L；K+：50.928g/L。在保温下继续往此溶液中加入固体氯化钠，使其饱和，分析饱和溶液成分组成为：Na+：100.386g/L；Cl-：223.353g/L；其它不变，在此条件下加入总抑制剂850g，自然降至室温，未发现明显结晶物出现。Na+ : 93.386g/L; Cl- : 215.35g/L; Ca2+ : 3.177g/L; Mg2+ : 3.726g/L; K+ : 50.928g/L. Continue to add solid sodium chloride to this solution under heat preservation to make it saturated. The composition of the saturated solution is analyzed as follows: Na+ : 100.386g/L; Cl- : 223.353g/L; other things remain unchanged, add The total inhibitor was 850g, and it was naturally cooled to room temperature, and no obvious crystals were found to appear.
实施例3：Example 3:
250kg乙二醇，110kg氨三乙酸一并加入并列的容积为2.5m3的工业反应釜，再缓缓各加入粗孔硅胶100kg，持续搅拌加热反应釜至200℃，恒温4小时，冷却至110℃，泄料口倾倒出粗孔硅胶，待反应混合物温度降到90℃时通过气体扩散器持续通入干燥的氨气直至温度降至35℃时停止通入氨气，所得浆状物过滤，甲醇洗涤，干燥，两釜产物合并得到产品氨三乙酰胺95kg，反复三次共制得产品氨三乙酰胺280kg，再加入乙二胺四乙酸四钠3.5kg，混匀得总抑制剂，备用。Add 250kg of ethylene glycol and 110kg of nitrilotriacetic acid into a parallel industrial reactor with a volume of 2.5m3 , then slowly add 100kg of coarse-pore silica gel, keep stirring and heat the reactor to 200°C, keep the temperature for 4 hours, and cool to 110°C ℃, pour out the coarse-pored silica gel from the discharge port, and when the temperature of the reaction mixture drops to 90°C, dry ammonia gas is continuously introduced through the gas diffuser until the temperature drops to 35°C, and the ammonia gas is stopped, and the resulting slurry is filtered. Wash with methanol, dry, and combine the products of the two kettles to obtain 95 kg of the product aminotriacetamide, and repeat three times to obtain a total of 280 kg of the product ammoniatriacetamide, then add 3.5 kg of tetrasodium ethylenediaminetetraacetic acid, mix well to obtain the total inhibitor, and set aside.
四川平落坝卤水出井口卤水温度102℃，离子组成为：Na+：93.386g/L；Cl-：215.35g/L；Ca2+：3.177g/L；Mg2+：3.726g/L；K+：50.928g/L。在出井口时按比例1-1.5：1000(固液比)连续加入至卤水中，迅速搅拌溶解，再输送至工厂，自然降至室温，未发现明显结晶物出现。The brine temperature at the wellhead of Pingluoba brine in Sichuan is 102°C, and the ion composition is: Na+ : 93.386g/L; Cl- : 215.35g/L; Ca2+ : 3.177g/L; Mg2+ : 3.726g/L; K+ : 50.928g/L. When it comes out of the wellhead, it is continuously added to the brine according to the ratio of 1-1.5:1000 (solid-to-liquid ratio), stirred and dissolved rapidly, and then transported to the factory, and naturally cooled to room temperature, and no obvious crystallization was found.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710195468.4ACN106957639A (en) | 2017-03-29 | 2017-03-29 | A kind of the easy of salt crystallization inhibitor synthesizes and its used |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710195468.4ACN106957639A (en) | 2017-03-29 | 2017-03-29 | A kind of the easy of salt crystallization inhibitor synthesizes and its used |
| Publication Number | Publication Date |
|---|---|
| CN106957639Atrue CN106957639A (en) | 2017-07-18 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710195468.4APendingCN106957639A (en) | 2017-03-29 | 2017-03-29 | A kind of the easy of salt crystallization inhibitor synthesizes and its used |
| Country | Link |
|---|---|
| CN (1) | CN106957639A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476982A (en)* | 2016-07-14 | 2019-03-15 | 朗盛解决方案美国公司 | High density clarified brine liquid |
| CN109734162A (en)* | 2018-08-15 | 2019-05-10 | 长沙湘朴科技有限公司 | Calcium chloride solution preparation method for the processing of fluorite ore beneficiation wastewater |
| CN110643333A (en)* | 2019-08-30 | 2020-01-03 | 成都理工大学 | Salt crystallization inhibitor for preventing sodium chloride crystallization in oil well and preparation method thereof |
| CN116589991A (en)* | 2023-07-11 | 2023-08-15 | 西南石油大学 | Salt recrystallization inhibitor for high-density brine completion fluid system and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274448A (en)* | 2013-06-19 | 2013-09-04 | 太仓沪试试剂有限公司 | Silver nitrate purifying method |
| CN104449604A (en)* | 2014-06-26 | 2015-03-25 | 武志学 | Solid-free well control fluid for borehole operation for low permeability reservoir and preparation method of solid-free well control fluid |
| CN105858688A (en)* | 2016-04-04 | 2016-08-17 | 黄冈师范学院 | Method for quickly converting NOx tail gas into potassium nitrate |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274448A (en)* | 2013-06-19 | 2013-09-04 | 太仓沪试试剂有限公司 | Silver nitrate purifying method |
| CN104449604A (en)* | 2014-06-26 | 2015-03-25 | 武志学 | Solid-free well control fluid for borehole operation for low permeability reservoir and preparation method of solid-free well control fluid |
| CN105858688A (en)* | 2016-04-04 | 2016-08-17 | 黄冈师范学院 | Method for quickly converting NOx tail gas into potassium nitrate |
| Title |
|---|
| 朱彬: "《有机合成》", 31 January 2014, 成都：西南交通大学出版社* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476982A (en)* | 2016-07-14 | 2019-03-15 | 朗盛解决方案美国公司 | High density clarified brine liquid |
| CN109734162A (en)* | 2018-08-15 | 2019-05-10 | 长沙湘朴科技有限公司 | Calcium chloride solution preparation method for the processing of fluorite ore beneficiation wastewater |
| CN110643333A (en)* | 2019-08-30 | 2020-01-03 | 成都理工大学 | Salt crystallization inhibitor for preventing sodium chloride crystallization in oil well and preparation method thereof |
| CN116589991A (en)* | 2023-07-11 | 2023-08-15 | 西南石油大学 | Salt recrystallization inhibitor for high-density brine completion fluid system and preparation method thereof |
| CN116589991B (en)* | 2023-07-11 | 2023-09-15 | 西南石油大学 | Salt recrystallization inhibitor for high-density brine completion fluid system and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
| CN106957639A (en) | A kind of the easy of salt crystallization inhibitor synthesizes and its used | |
| CN102060312B (en) | Method and device for preventing bittern delivery pipeline from scaling | |
| CN102634843A (en) | Method for preparing micron-sized calcium sulfate particles and crystal whiskers from phosphogypsum | |
| CN101654611A (en) | Method for manufacturing snowmelt agent by using shells | |
| CN103342988A (en) | Environment-friendly snow melting agent and preparation method thereof | |
| CN104192918A (en) | Sewage treatment agent and preparation method and application thereof | |
| CN108467718A (en) | A kind of preparation of water filling with antisepsis clay expansion-resisting agent | |
| CN108467719A (en) | A kind of preparation with sterilization and the water filling clay expansion-resisting agent of anti-scaling action | |
| CN105462569B (en) | A kind of preparation method of oil/gas well salt recrystallization inhibition agent | |
| CN105036161A (en) | Preparation method of magnesium carbonate crystal | |
| CN105271880B (en) | Cement grinding aid | |
| KR20130025603A (en) | Deicing agent in a liquid phase | |
| CN112111039B (en) | Dispersing agent, preparation method and application thereof | |
| US11311036B2 (en) | Synthetic base and associated methods | |
| RU2323244C1 (en) | Method of preparing solid foaming agent for removing liquid from gas or gas condensate wells | |
| CN107522219A (en) | A kind of preparation method of industrial calcium chloride | |
| CN106007797B (en) | Cement-based penetrant curing agent | |
| CN100595254C (en) | A kind of preparation method of zwitterionic polymer fluid loss reducer | |
| CN100509992C (en) | Method for preparing ternary composite drive-collect-convey system anti-deposition agent | |
| CN104828846B (en) | The method for being purified using high-temperature bittern and separating lithium carbonate mixed salt | |
| EP4570786A2 (en) | Crystalline form of 2-acrylamido-2-methylpropanesulphonic acid potassium salt | |
| US2610899A (en) | Pipeline transportation of soluble granular materials | |
| CN102659141A (en) | Preparation method for branch salt | |
| Haiyan et al. | Preparation and application of new polycarboxylic acid for scale inhibition | |
| CN117023816A (en) | High-salt natural gas produced water scale inhibitor and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20170718 |