TWI708835B - Slow release type carbon-releasing gel substrate and soil treatment method - Google Patents
Slow release type carbon-releasing gel substrate and soil treatment method Download PDFInfo
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本發明係關於一種凝膠基質及土壤整治方法，特別是關於一種緩釋型釋碳凝膠基質及土壤整治方法。The invention relates to a gel matrix and a soil remediation method, in particular to a slow-release carbon releasing gel matrix and a soil remediation method.
含氯有機溶劑常被廣泛應用於脫脂、電子零件清洗及乾洗等工業製程中，常因人為不當管理與處置，而使含氯有機溶劑外洩成為地下水中常見之重質非水相溶液(dense non-aqueous phase liquids, DNAPL)污染物，由於重質非水相溶液之密度比水重且與水不相溶或僅微溶於水，因此重質非水相溶液進入地下水層後會形成一獨立之液相，而三氯乙烯(trichloroethylene, TCE)則為國內外最具代表性之含氯有機溶劑。一旦發生三氯乙烯洩漏，將可能經由飲用水等多種途徑暴露到環境中，對鄰近民眾之健康造成嚴重危害。Chlorine-containing organic solvents are often widely used in industrial processes such as degreasing, electronic parts cleaning and dry cleaning. Often due to improper management and disposal by humans, the leakage of chlorinated organic solvents has become a common heavy non-aqueous solution in groundwater. non-aqueous phase liquids, DNAPL) pollutants, because the density of heavy non-aqueous phase liquids is heavier than water and incompatible with water or only slightly soluble in water, so heavy non-aqueous phase liquids will form a Independent liquid phase, and trichloroethylene (TCE) is the most representative chlorinated organic solvent at home and abroad. Once a trichloroethylene leak occurs, it may be exposed to the environment through various channels such as drinking water, causing serious harm to the health of neighboring people.
為解決上述污染問題，許多研究即以三氯乙烯為目標污染物，以研究發展可處理DNAPL污染地下水之整治技術。例如，使用化學還原法、奈米技術及微生物應用在生物整治來降解環境中的含氯有機污染物已經有數十年的研究與應用，其中屬於綠色整治之生物復育程序(bioremediation)是屬於對環境較友善且較為迅速的技術，其應用於現地降解環境污染物主要是提供生物可降解之有機基質組成物予現地微生物以輔助微生物分解污染物，因此相較於物理與化學整治之方法可以相對降低整治成本，容易操作且較易受社會大眾接受，同時生物復育程序降解過程中也較沒有轉變污染物型態如化學沉澱以及產生大量有害污泥等對環境造成二次傷害的疑慮。In order to solve the above-mentioned pollution problems, many studies have focused on trichloroethylene as the target pollutant to research and develop remediation technologies that can treat DNAPL contaminated groundwater. For example, the use of chemical reduction methods, nanotechnology and microbial applications in bioremediation to degrade chlorinated organic pollutants in the environment has been researched and applied for decades. Among them, the bioremediation program of green remediation belongs to Environmentally friendly and rapid technology, its application in the on-site degradation of environmental pollutants is mainly to provide biodegradable organic matrix composition to the on-site microorganisms to assist the microorganisms in decomposing the pollutants, so it can be compared with physical and chemical treatment methods. Relatively lower remediation costs, easy to operate and easier to be accepted by the general public. At the same time, the degradation process of the biological restoration process is less likely to change the types of pollutants such as chemical precipitation and produce a large amount of harmful sludge that will cause secondary damage to the environment.
然而，現有生物整治的方法並未有針對於地下水流速較快之污染場址，因而無法持續產生整治效果。故，有必要提供一種緩釋型釋碳凝膠基質及土壤整治方法，以解決習用技術所存在的問題。However, the existing biological remediation methods are not targeted at contaminated sites with a faster groundwater flow rate, and therefore cannot continue to produce remediation effects. Therefore, it is necessary to provide a slow-release carbon-releasing gel matrix and a soil remediation method to solve the problems existing in the conventional technology.
本發明之一目的在於提供一種緩釋型釋碳凝膠基質及土壤整治方法，其通過使用特定的油品及凝膠劑，以使緩釋型釋碳凝膠基質能停留在目標污染區的土壤孔隙間，並於注藥區形成一透水性生物整治牆。除可有效於污染區持續釋碳供現地可降解污染物之微生物利用外，亦可阻斷和局限殘留之污染物，避免其持續移動至飽和含水層。One purpose of the present invention is to provide a slow-release carbon-releasing gel matrix and a soil remediation method, which uses specific oils and gels so that the slow-release carbon-releasing gel matrix can stay in the target polluted area. A water-permeable biological remediation wall is formed between the soil pores and in the injection area. In addition to effective continuous release of carbon in the polluted area for the utilization of microorganisms that can degrade pollutants, it can also block and limit the remaining pollutants to prevent them from continuously moving to the saturated aquifer.
為達上述的目的，本發明提供一種緩釋型釋碳凝膠基質，包含：30至40重量份的椰子油；5至10重量份的卵磷脂；2至5重量份的界面活性劑；0.1至0.5重量份的凝膠劑；及40至50重量份的水。In order to achieve the above objective, the present invention provides a sustained-release carbon release gel matrix, comprising: 30 to 40 parts by weight of coconut oil; 5 to 10 parts by weight of lecithin; 2 to 5 parts by weight of surfactant; 0.1 To 0.5 parts by weight of gelling agent; and 40 to 50 parts by weight of water.
在本發明一實施例中，該卵磷脂包含大豆卵磷脂。In an embodiment of the present invention, the lecithin comprises soybean lecithin.
在本發明一實施例中，該凝膠劑包含明膠、瓊脂及鹿角菜膠中的至少一種。In an embodiment of the present invention, the gelling agent includes at least one of gelatin, agar, and carrageenan.
在本發明一實施例中，該緩釋型釋碳凝膠基質還包含0.1至1重量份的乳酸鈉。In an embodiment of the present invention, the sustained-release carbon release gel matrix further contains 0.1 to 1 part by weight of sodium lactate.
在本發明一實施例中，該緩釋型釋碳凝膠基質還包含0.1至1重量份的維生素。In an embodiment of the present invention, the sustained-release carbon-release gel matrix further contains 0.1 to 1 parts by weight of vitamins.
為達上述的目的，本發明提供一種土壤整治方法，包含步驟：提供如上所述的任一實施例的緩釋型釋碳凝膠基質；及注入該緩釋型釋碳凝膠基質至一待整治土壤中。In order to achieve the above objective, the present invention provides a soil remediation method, including the steps of: providing the sustained-release carbon-releasing gel matrix of any one of the embodiments described above; and injecting the sustained-release carbon-releasing gel matrix into a waiting room. Remediate the soil.
在本發明一實施例中，提供該緩釋型釋碳凝膠基質的步驟包含：混合30至40重量份的椰子油、5至10重量份的卵磷脂、2至5重量份的界面活性劑及40至50重量份的水，以形成一乳化液；加入0.1至0.5重量份的凝膠劑至該乳化液中，以形成一前處理液；及對該前處理液進行一均勻混合步驟，以形成該緩釋型釋碳凝膠基質。In an embodiment of the present invention, the step of providing the sustained-release carbon release gel matrix includes: mixing 30 to 40 parts by weight of coconut oil, 5 to 10 parts by weight of lecithin, and 2 to 5 parts by weight of surfactant And 40 to 50 parts by weight of water to form an emulsion; add 0.1 to 0.5 parts by weight of gelling agent to the emulsion to form a pre-treatment liquid; and perform a uniform mixing step on the pre-treatment liquid, To form the sustained-release carbon-release gel matrix.
在本發明一實施例中，提供該均勻混合步驟包含通過一均質裝置以10000至15000RPM的一轉速均勻混合該前處理液。In an embodiment of the present invention, providing the uniform mixing step includes uniformly mixing the pre-treatment liquid at a rotation speed of 10,000 to 15,000 RPM through a homogenizing device.
為了讓本發明之上述及其他目的、特徵、優點能更明顯易懂，下文將特舉本發明較佳實施例，並配合所附圖式，作詳細說明如下。再者，本發明所提到的方向用語，例如上、下、頂、底、前、後、左、右、內、外、側面、周圍、中央、水平、橫向、垂直、縱向、軸向、徑向、最上層或最下層等，僅是參考附加圖式的方向。因此，使用的方向用語是用以說明及理解本發明，而非用以限制本發明。In order to make the above and other objects, features, and advantages of the present invention more obvious and understandable, the following will specifically cite the preferred embodiments of the present invention, together with the accompanying drawings, and describe in detail as follows. Furthermore, the directional terms mentioned in the present invention, such as up, down, top, bottom, front, back, left, right, inside, outside, side, surrounding, center, horizontal, horizontal, vertical, vertical, axial, The radial direction, the uppermost layer or the lowermost layer, etc., are only the direction of reference to the attached drawings. Therefore, the directional terms used are used to describe and understand the present invention, rather than to limit the present invention.
本發明一實施例之緩釋型釋碳凝膠基質包含：30至40重量份的椰子油；5至10重量份的卵磷脂；2至5重量份的界面活性劑；0.1至0.5重量份的凝膠劑；及40至50重量份的水。在一實施例中，椰子油例如是可供食用的市售椰子油或者已經使用過的廢棄食用油。椰子油是一種食用油，當食用油以乳化型態注入土壤時，其液滴細小且均勻，因此更容易擴散至不同種類之土壤孔隙間。當食用油注入至地下含水層時，三酸甘油脂會經由厭氧發酵水解出甘油(醇類)和長鏈脂肪酸(Long-Chain Fatty Acids, LCFAs)，由於甘油具有生物分解性且易溶於水，因此當甘油存在於土壤中時，則會被快速分解或刺激微生物。因此，椰子油主要可作為碳源，以提供予待整治土壤的微生物。另一方面，由於椰子油本身具備感溫性，於24℃以下開始出現結晶與凝固之現象。因此，通過利用椰子油因溫度差異而相轉變之特性，本發明一實施例之緩釋型釋碳凝膠基質藥劑可於地下環境中傳輸且有效停留於污染區之土壤孔隙間。在另一實施例中，椰子油例如可以是31、32、33、34、35、36、37、38或39重量份。The sustained-release carbon release gel matrix of an embodiment of the present invention comprises: 30 to 40 parts by weight of coconut oil; 5 to 10 parts by weight of lecithin; 2 to 5 parts by weight of surfactant; 0.1 to 0.5 parts by weight Gel; and 40 to 50 parts by weight of water. In one embodiment, the coconut oil is, for example, commercially available coconut oil that is edible or waste edible oil that has been used. Coconut oil is a kind of edible oil. When edible oil is injected into the soil in an emulsified form, its droplets are small and uniform, so it is easier to diffuse into the pores of different types of soil. When edible oil is injected into underground aquifers, triglycerides will be hydrolyzed into glycerol (alcohols) and long-chain fatty acids (LCFAs) through anaerobic fermentation. Because glycerol is biodegradable and easily soluble Water, so when glycerin is present in the soil, it will be quickly broken down or stimulate microorganisms. Therefore, coconut oil can mainly be used as a carbon source to provide microorganisms in the soil to be rehabilitated. On the other hand, due to the temperature sensitivity of coconut oil, crystallization and solidification begin to appear below 24°C. Therefore, by taking advantage of the phase transition characteristics of coconut oil due to temperature differences, the slow-release carbon-releasing gel matrix medicament of an embodiment of the present invention can be transported in the underground environment and effectively stay in the soil pores in the contaminated area. In another embodiment, the coconut oil may be 31, 32, 33, 34, 35, 36, 37, 38, or 39 parts by weight, for example.
在一實施例中，該卵磷脂可包含大豆卵磷脂。在另一實施例中，卵磷脂例如可以是6、7、8或9重量份。卵磷脂可做為界面活性劑。In one embodiment, the lecithin may include soy lecithin. In another embodiment, the lecithin may be 6, 7, 8, or 9 parts by weight, for example. Lecithin can be used as a surfactant.
在一實施例中，該界面活性劑主要作為乳化油品的效果。在一範例中，該界面活性劑例如是市售的界面活性劑(例如SUNSHINE MAKERS公司出品的SIMPLE GREEN品牌的界面活性劑)。在另一實施例中，該界面活性劑例如可以是3、3.5、4或4.5重量份。In one embodiment, the surfactant is mainly used as an emulsified oil product. In one example, the surfactant is, for example, a commercially available surfactant (for example, a SIMPLE GREEN brand of surfactant produced by SUNSHINE MAKERS). In another embodiment, the surfactant may be 3, 3.5, 4, or 4.5 parts by weight, for example.
在一實施例中，該凝膠劑包含明膠、瓊脂及鹿角菜膠中的至少一種。在一範例中，該凝膠劑是瓊脂。瓊脂(arga)為一種天然高分子膠，當溫度降低時，瓊脂具有呈鏈狀分散之高分子網狀結構，分散介質水被全部包含在網狀結構之中，形成了不流動之半固體凝膠形態。但值得一提的是，上述的明膠與鹿角菜膠亦具備類似的效果。在另一實施例中，凝膠劑例如可以是0.2、0.3或0.4重量份。In one embodiment, the gelling agent includes at least one of gelatin, agar, and carrageenan. In one example, the gel is agar. Agar (arga) is a kind of natural polymer glue. When the temperature is lowered, the agar has a polymer network structure with chain-like dispersion. The dispersion medium water is all contained in the network structure, forming a non-flowing semi-solid gel. Glue form. But it is worth mentioning that the above-mentioned gelatin and carrageenan also have similar effects. In another embodiment, the gelling agent may be 0.2, 0.3 or 0.4 parts by weight, for example.
在一實施例中，水主要作為溶劑，以使緩釋型釋碳凝膠基質形成一溶液態。在另一實施例中，水例如可以是41、42、43、44、45、46、47、48或49重量份。In one embodiment, water is mainly used as a solvent to make the sustained-release carbon release gel matrix form a solution state. In another embodiment, the water may be 41, 42, 43, 44, 45, 46, 47, 48, or 49 parts by weight, for example.
在一實施例中，該緩釋型釋碳凝膠基質還包含0.1至1重量份的乳酸鈉。乳酸鈉可作為輔助的生物碳源，以提供予待整治土壤的微生物。在另一實施例中，乳酸鈉例如可以是0.2、0.3、0.4、0.5、0.6、0.7、0.8或0.9重量份。In one embodiment, the sustained-release carbon release gel matrix further contains 0.1 to 1 part by weight of sodium lactate. Sodium lactate can be used as an auxiliary biological carbon source to provide microorganisms in the soil to be rehabilitated. In another embodiment, sodium lactate may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 parts by weight, for example.
在一實施例中，該緩釋型釋碳凝膠基質還包含0.1至1重量份的維生素。維生素可作為微量營養素，以提供予待整治土壤的微生物。在另一實施例中，維生素例如可以是0.2、0.3、0.4、0.5、0.6、0.7、0.8或0.9重量份。In one embodiment, the sustained-release carbon-release gel matrix further contains 0.1 to 1 parts by weight of vitamins. Vitamins can be used as micronutrients to provide microorganisms in the soil to be rehabilitated. In another embodiment, the vitamin may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 parts by weight, for example.
要提到的是，本發明實施例之緩釋型釋碳凝膠基質至少是通過加入特定的油品(例如椰子油)以及凝膠劑所產生的綜合效果，以使緩釋型釋碳凝膠基質能夠持續停留在於污染區之土壤孔隙間，以改善地下水流速較快造成之基質流失之問題，形成可透水性生物整治牆，持續緩釋碳源供現地微生物利用，可降低注藥成本。It should be mentioned that the sustained-release carbon-releasing gel matrix of the embodiment of the present invention is at least the combined effect of adding specific oils (such as coconut oil) and gels to make the sustained-release carbon-release coagulation The glue matrix can stay in the pores of the soil in the contaminated area to improve the problem of matrix loss caused by the faster groundwater flow rate, form a water-permeable biological remediation wall, and continuously release the carbon source for the use of local microorganisms, which can reduce the cost of injection.
另外要提到的是，本發明實施例之緩釋型釋碳凝膠基質至少是通過使用特定比例的特定組成物，以使緩釋型釋碳凝膠基質能夠持續停留在於污染區之土壤孔隙間，以改善地下水流速較快造成之基質流失之問題。在後續的實驗結果可證明，即便已經置換15孔隙體積(PV)的水體，仍可持續釋出大量的總有機碳(total organic carbon；TOC)。上述的結果說明，凝膠基質可有效停留於土壤孔隙間，不易因水流速度過快而流失，並可於現地環境持續釋出碳源以供現地微生物生長所需，適合用於高流速場址，以減少藥劑流失及降低成本。In addition, it should be mentioned that the sustained-release carbon-releasing gel matrix of the embodiment of the present invention at least uses a specific composition of a specific ratio to enable the sustained-release carbon-release gel matrix to stay in the soil pores in the contaminated area. Space to improve the problem of matrix loss caused by faster groundwater flow. Subsequent experimental results can prove that even if a water body of 15 pore volume (PV) has been replaced, a large amount of total organic carbon (TOC) can still be released continuously. The above results indicate that the gel matrix can effectively stay in the pores of the soil, is not easy to be lost due to the excessively fast water flow rate, and can continuously release carbon sources in the on-site environment for the growth of on-site microorganisms, which is suitable for high-velocity sites , In order to reduce the loss of medicine and reduce costs.
請參照第1圖，本發明一實施例之土壤整治方法10，主要包含下列步驟11至12：提供本發明任一實施例的緩釋型釋碳凝膠基質(步驟11)；及注入該緩釋型釋碳凝膠基質至一待整治土壤中(步驟12)。Please refer to Figure 1, the
在一實施例中，提供該緩釋型釋碳凝膠基質的步驟包含：混合30至40重量份的椰子油、5至10重量份的卵磷脂、2至5重量份的界面活性劑及40至50重量份的水，以形成一乳化液；加入0.1至0.5重量份的凝膠劑至該乳化液中，以形成一前處理液；及對該前處理液進行一均勻混合步驟，以形成該緩釋型釋碳凝膠基質。在一範例中，該均勻混合步驟包含通過一均質裝置(例如一市售均質機)以10000至15000RPM的一轉速均勻混合該前處理液。In one embodiment, the step of providing the sustained-release carbon release gel matrix includes: mixing 30 to 40 parts by weight of coconut oil, 5 to 10 parts by weight of lecithin, 2 to 5 parts by weight of a surfactant, and 40 parts by weight. To 50 parts by weight of water to form an emulsion; add 0.1 to 0.5 parts by weight of gelling agent to the emulsion to form a pre-treatment liquid; and perform a uniform mixing step on the pre-treatment liquid to form The sustained-release carbon-release gel matrix. In one example, the uniform mixing step includes uniformly mixing the pre-treatment liquid at a rotation speed of 10,000 to 15,000 RPM through a homogenizer (such as a commercially available homogenizer).
以下舉出一實施例，以說明本發明實施例之緩釋型釋碳凝膠基質確實能停留在目標污染區的土壤孔隙間。An example is given below to illustrate that the slow-release carbon-releasing gel matrix of the embodiment of the present invention can indeed stay in the soil pores of the target contaminated area.
實施例1Example 1
首先，混合30至40重量份的椰子油、5至10重量份的卵磷脂(例如大豆卵磷脂)、2至5重量份的界面活性劑(例如SUNSHINE MAKERS公司出品的SIMPLE GREEN品牌的界面活性劑)及40至50重量份的水，以形成一乳化液。接著，加入0.1至0.5重量份的凝膠劑(例如瓊脂)至該乳化液中，以形成一前處理液。通過一均質裝置以10000至15000RPM(例如12000RPM)的一轉速均勻混合該前處理液，以形成該緩釋型釋碳凝膠基質。First, mix 30 to 40 parts by weight of coconut oil, 5 to 10 parts by weight of lecithin (such as soybean lecithin), and 2 to 5 parts by weight of surfactant (such as SIMPLE GREEN brand surfactant produced by SUNSHINE MAKERS) ) And 40 to 50 parts by weight of water to form an emulsion. Then, 0.1 to 0.5 parts by weight of gelling agent (for example, agar) is added to the emulsion to form a pre-treatment liquid. The pretreatment liquid is uniformly mixed at a rotation speed of 10,000 to 15,000 RPM (for example, 12,000 RPM) through a homogenizing device to form the sustained-release carbon release gel matrix.
之後，注入該緩釋型釋碳凝膠基質至一待整治土壤中，並且通過市售儀器測量置換水體程度與總有機碳的釋放關係。所得分析結果如第2圖所示，其中C0指的是初始總有機碳濃度，以及C指的是置換各種孔隙體積後的總有機碳濃度。從第2圖可知，當水體已置換15孔隙體積(PV)時，仍可持續釋出大量的總有機碳(total organic carbon；TOC)，說明凝膠基質可有效停留於土壤孔隙間，不易因水流速度過快而流失，並可於現地環境持續釋出碳源以供現地微生物生長所需，適合用於高流速場址，以減少藥劑流失及降低成本。Then, the slow-release carbon release gel matrix is injected into a soil to be renovated, and the relationship between the degree of replacement of water and the release of total organic carbon is measured by a commercially available instrument. The obtained analysis results are shown in Figure 2, where C0 refers to the initial total organic carbon concentration, and C refers to the total organic carbon concentration after replacing various pore volumes. It can be seen from Figure 2 that when the water body has replaced 15 pore volumes (PV), a large amount of total organic carbon (TOC) can still be released continuously, indicating that the gel matrix can effectively stay in the pores of the soil, which is not easy to cause. The water flow rate is too fast and it is lost, and the carbon source can be continuously released in the local environment for the growth of local microorganisms. It is suitable for high-velocity sites to reduce the loss of chemicals and reduce costs.
雖然本發明已以較佳實施例揭露，然其並非用以限制本發明，任何熟習此項技藝之人士，在不脫離本發明之精神和範圍內，當可作各種更動與修飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be subject to the scope of the attached patent application.
10…方法
11~12…步驟10...
第1圖是本發明一實施例之土壤整治方法的流程示意圖。 第2圖是實施例1的分析結果圖。Figure 1 is a schematic flow chart of a soil improvement method according to an embodiment of the present invention. Figure 2 is a graph showing the analysis results of Example 1.
10:方法 10: method
11~12:步驟 11~12: steps
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| US5929030A (en) * | 1995-08-30 | 1999-07-27 | Byron Fine Chemicals Inc. | Pharmaceutical compositions |
| WO2006132042A1 (en) * | 2005-06-10 | 2006-12-14 | Yasuyuki Yamada | Nutritional supplement powder and fat for food or medicine |
| CN101636439A (en) * | 2007-02-01 | 2010-01-27 | 不列颠哥伦比亚大学 | The method of drying biological material |
| WO2013009448A1 (en) * | 2011-07-08 | 2013-01-17 | Clinavenir, Llc | Topical formulations containing palm pollen |
| US8877469B2 (en) * | 2004-07-30 | 2014-11-04 | Enwave Corporation | Method of drying biological material |
| US20150057342A1 (en) * | 2013-08-21 | 2015-02-26 | Cannabics Pharmaceuticals Inc | Compositions for combined immediate and sustained release of cannabinoids, methods of manufacture and use thereof |
| WO2017095736A1 (en) * | 2015-12-01 | 2017-06-08 | R.P. Scherer Technologies, Llc | Aspirin soft gelatin capsule as a single active or in combination with other actives |
| WO2017208072A2 (en) * | 2016-06-02 | 2017-12-07 | Acerus Pharmaceutical Corporation | Nasal cannabidiol compositions |
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Patent Citations (10)
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|---|---|---|---|---|
| US5929030A (en) * | 1995-08-30 | 1999-07-27 | Byron Fine Chemicals Inc. | Pharmaceutical compositions |
| US8877469B2 (en) * | 2004-07-30 | 2014-11-04 | Enwave Corporation | Method of drying biological material |
| WO2006132042A1 (en) * | 2005-06-10 | 2006-12-14 | Yasuyuki Yamada | Nutritional supplement powder and fat for food or medicine |
| CN101636439A (en) * | 2007-02-01 | 2010-01-27 | 不列颠哥伦比亚大学 | The method of drying biological material |
| EP2111426B1 (en) * | 2007-02-01 | 2017-10-04 | EnWave Corporation | Method of drying biological material |
| WO2013009448A1 (en) * | 2011-07-08 | 2013-01-17 | Clinavenir, Llc | Topical formulations containing palm pollen |
| US20160331677A1 (en) * | 2011-07-08 | 2016-11-17 | Clinavenir, Llc | Topical Formulations Containing Palm Pollen |
| US20150057342A1 (en) * | 2013-08-21 | 2015-02-26 | Cannabics Pharmaceuticals Inc | Compositions for combined immediate and sustained release of cannabinoids, methods of manufacture and use thereof |
| WO2017095736A1 (en) * | 2015-12-01 | 2017-06-08 | R.P. Scherer Technologies, Llc | Aspirin soft gelatin capsule as a single active or in combination with other actives |
| WO2017208072A2 (en) * | 2016-06-02 | 2017-12-07 | Acerus Pharmaceutical Corporation | Nasal cannabidiol compositions |
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