This time, the new version of the "Pharmaceutical Production License", "Medical Organization Preparation License", "Pharmaceutical Business License", "Radioactive Drug Production License", "Radioactive Drugs Business License" and "Use of Radioactive Drugs" uniformly formulated by the State Food and Drug Administration are included. License: "Internet Drug Information Service Qualification Certificate" (including positive and duplicate) and other seven certificates.

For the licenses that have not expired in 2019, the provincial (autonomous regions, municipalities) Drug Administration will organize the replacement of the new licenses by the end of December 2020, and the validity period is the same as the original certificate. If the requirements are not met, no replacement will be given.

The reason for the increase in the price of potassium sulphate in the early stage was mainly due to the overall low start of the potassium sulphate industry, the increase in export volume and the application of water-soluble fertilizer. At present, the summer demand for water-soluble fertilizers has gradually ended, and some parts of the autumn and winter season have entered the market for water-soluble fertilizers. In the traditional off-season, in addition, some time ago, the typhoon “Litchma” landed, and floods in some areas frequently occurred, which made the downstream planting enthusiasm weaken. As the demand for water-soluble fertilizer decreased, the corresponding 52% water-soluble potassium sulfate was lacking. Strong support. Recently, Mannheim enterprises are expecting to place orders before the implementation, but the new single transaction atmosphere is not good. Although the factory offer is firmer, the transaction price has begun to loosen with the increase of the inventory in the factory.

Although the recent demand has weakened, this year's export of potassium sulphate is still considerable, and although Mannheim's industry stocks have increased, it is still shipping pre-orders, and there is no obvious inventory pressure. In the second half of the year, the demand for tobacco fertilizer has a certain positive effect on potassium sulfate. It is understood that although Fujian Tobacco Tendering has experienced the flow label re-flowing standard, it was finally won by Luo Potassium at a price of 2,950 yuan.

From the perspective of cost, the trend of potassium chloride in the first half of the year has been going down all the way, and the overall trend is bearish. However, the situation of environmental protection upgrade pressure and hydrochloric acid lodging is severe, the overall operating rate of enterprises is not high, and the downward price of potassium sulfate price is limited.

On the whole, there is no obvious positive and negative situation in the domestic potassium sulfate market. Although the price has a downward trend, the range is limited. It is difficult to have obvious fluctuations in the short term. It is recommended to pay more attention to the downstream demand situation and the start of the operation of the potassium sulfate enterprises.

The cause of the recent reduction of urea: on the one hand, because the overall trend of the market is relatively poor, the market price competition is relatively fierce, and the cost pressure of some enterprises with relatively high production costs is too large, and they are unwilling to carry out a lower price war. The operating costs, some enterprises can only temporarily enter the shutdown phase to ease; on the other hand, individual enterprises have not systematically overhauled the equipment from the beginning of the year, in order to ensure the normal operation of the equipment and prepare for the later winter storage market, The stage temporarily enters the inspection. Considering the activities of the National Day military parade in October, it is expected that the overall supply of urea around mid-September will be further reduced.

However, the supply reduction of urea has not injected significant vitality into the downturn market of urea. The price competition among enterprises is still relatively fierce. The main reason is that market demand is relatively weak. After the implementation of international export orders, there is no The new singles follow-up, and the international market prices are lower, and the enthusiasm of enterprises for export is relatively poor. However, the demand for the grassroots market in the domestic market is over, and the raw materials to be consumed by the compound fertilizer enterprises are relatively abundant, while the board manufacturers are also exporting. Bad news such as the overall shutdown of the region, the urea market demand is relatively low, even if the current supply is slightly reduced, but the pressure remains.

In summary, the demand for urea in the near future is relatively poor, while the market demand in Xinjiang is relatively small. The time for the externally issued factory price to fall below 1,300 yuan should not be too far away. At that time, the urea prices in the southwest and northwest regions will still be further affected. Impact, affected by this, the price of low-priced urea in Inner Mongolia and Shanxi should not be too optimistic, it is expected that the urea market should not have a substantial increase before mid-September.

According to customs statistics, in July 2019, China's export volume of monoammonium phosphate was about 318,300 tons. The total export volume in January-July was about 1.7 million tons, an increase of about 461,900 tons, an increase of about 37.31%.
In July 2019, China exported 554 million tons of Brazil's MAP, accounting for about 32% of total exports; compared with 431,300 tons in the same period of 2018, it increased by about 127,700 tons, an increase of 28.45%, accounting for about 34.90% of total exports. Although the volume of exports to Brazil increased in July, its total share fell by 2.9%.

From January to June 2019, Brazil imported about 1.4 million tons of MAP, an increase of nearly 500,000 tons from 2018. Sources of supply: 1, Morocco 407,000 tons, accounting for 28%; 2, Russia 737,000 tons, accounting for 26%; 3, the United States 306,000 tons, accounting for 21%; 4, Saudi Arabia 236,000 tons, accounting for 16%. It can be seen that Morocco's MAP has the biggest impact on China's exports, because the transportation distance is close (in the case of 50,000 tons of ships, the cost of Morocco to Brazil is about 18.5 US dollars / ton; while China is up to about 10 US dollars / ton. Nearby), the cost is low, and the pressure of Chinese supply export competition will continue to increase.

2. Overview of domestic supply and demand of monoammonium phosphate

According to statistics, the operating rate of domestic monoammonium phosphate was 54.35% as of last Friday, which was about 6.65% lower than that of the same period last year. The Hubei plant is operating normally, but it is reported that some of the daily output is reduced by half; the operating rate of the southwestern plant is low, of which the 55 powder plant of Guizhou Dachang is shut down, and the other plant plans to stop production of 60 powder to industrial grade; another plant in Sichuan is still only Open a production line.
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The downstream compound fertilizer enterprise operating rate was 48.7%. Among them, the northeast region is still in the off-season, and there is no obvious fluctuation in construction. Some factories in Central China and East China have started to improve compared with last week. Due to the influence of National Day military parade and environmental inspection, the manufacturers are actively producing pre-shipment orders and the weather. Some enterprises have resumed production in the high-tower facilities of the cooling industry. At present, the domestic construction is at a high level, and it is difficult to start construction in the short term.

At present, the domestic single-exchange volume of monoammonium phosphate market continues to be meager, and the downstream compound fertilizer large-scale enterprises have sufficient raw materials to stock up, and a small amount of out-of-stocks is insufficient to affect the market. In addition, due to the pressurization of finished products, it is reported that individual compound fertilizer enterprises have suspended raw materials. The one-ammonium factory shipped it; although the start-up of small-scale compound fertilizers was gradually improved, but the amount of raw materials used with the mining, the local traders have sufficient supply in their hands, and the price is not high, 55 powder is ex-factory price 1900-1950 yuan / ton, compared with the beginning of the year fell 240 yuan / ton.

3. Summary and forecast

Although the export volume increased year-on-year, the average monthly price of monoammonium phosphate exports fell by about US$30/ton in July; and the MAP price in Brazil fell another US$5/ton to US$335-340/ton CFR, and if the export price in September Still weak, Chinese suppliers will transfer most of their products to the domestic winter storage market, and domestic supply will continue to increase. However, as far as the domestic autumn market is concerned, even if the downstream compound fertilizer is available again, the supply of goods is sufficient. Therefore, there may be a wave of supply flow improvement in September, but the price is difficult to rise. In the short term, there are still 10-30. Yuan/ton drop.

When it comes to the migration of ions, the migration of lithium ions is necessary for the electrode reaction of lithium batteries. Because hexafluorophosphate does not participate in the electrode reaction, its movement does not contribute to the electrode reaction, but it does not contribute to the electrode reaction. Migration. What really contributes to battery performance is the migration of lithium ions. The amount of charge transferred by the amount of charge transferred by the total charge of the anion and cation is the number of lithium ions. The higher the number of migrations, the more the lithium ion accomplishes its mission. The higher the efficiency, the better for the electrode reaction. However, since the anion directly affects the solubility and dissociation ability of the lithium salt in the solution, thereby affecting the concentration and conductivity of the electrolyte, the applicable anion selection is not too much, in addition, different The cost of anion is not the same. In fact, we can do a lot of work on the number of migrations, or the actual decision to use the lithium salt is not determined by the size of the migration, but by other factors determined by the anion. Indicators such as solubility/cost/conductivity.

If the number of carbon atoms in the alkyl group increases, the polarity and molecular weight of the linear carbonate change, the viscosity and boiling point of the linear carbonate increase, and the solubility of the lithium salt decreases accordingly. Therefore, linear esters have a range to choose from. However, when a single alkyl group has more than three carbon atoms, the carbonate becomes less useful. It is more and more like an alkane solvent, and the solubility of the lithium salt is rapidly deteriorated, making it difficult to achieve practical use of the lithium salt. In the range of this, such esters are not suitable as a solvent. For example, when dipropyl carbonate and methyl propyl carbonate are added to the electrolyte, their compatibility with other carbonates and the solubility of lithium salts will be significantly reduced. In the case of temperature reduction, this situation More prominent.

Therefore, the linear esters in the electrolyte, we rarely see carbonates containing butyl or even pentyl; in general, the presence of propyl has been somewhat difficult. In the same molecule, the more the large alkyl groups, the more obvious this tendency. Therefore, dipropyl carbonate is not as good as the methyl propyl carbonate.

Linear carbonates also have an interesting phenomenon. From DMC to EMC to DEC, as the molecular weight increases, the density of the solvent decreases. The density of DMC is slightly greater than water, 1.063g/ml, EMC is 1.012 g/ml and water is very close, DEC is 0.969 g/ml, which is lighter than water. If you use water to kill carbonates, be aware that they are very similar to the density of water, and you may have to cover them with foam. Of course, after the electrolyte is formulated, the density of the electrolyte is significantly greater than that of water due to the addition of the cyclic ester and the lithium salt, and is usually above 1.2 g/ml.

Alkyl carbonates are odorous. According to our experience, DMC has a relatively low odor, and EMC and DEC have a relatively large odor. Therefore, when DMC is used as the solvent, although the volatility of DMC is greater than EMC (which is also an advantage), its odor is small (smaller than the odor of ethyl acetate) and relatively more popular. DMC's solubility is also very strong, and it has the ability to dissolve paint, marker, pressure-sensitive adhesive, inkjet printer ink, and also has a effect on the lithium salt after the electrolyte residue is volatilized. However, it should be noted that both DMC and EMC are typical Class A flammable solvents, and care should be taken to prevent static electricity and prevent deflagration. Another advantage of using DMC is that DMC is much cheaper and more cost effective than EMC and DEC. At the same time, DMC is also a green solvent, which is not as toxic as solvents such as aromatic hydrocarbons, cyclohexanes and acetone.

From the melting point point of view, DMC is higher than EMC and higher than DEC; from the viscosity point of view, DMC is smaller than EMC and smaller than DEC, so the effect of improving the conductivity is that DMC is superior to EMC and superior to DEC. However, if you compare the low-temperature charge and discharge performance, it is often the best EMC, followed by DMC, DEC again. The main reason is that EMC has a lower freezing point and a lower low temperature viscosity at low temperatures, resulting in better overall performance at low temperatures. DMC has a high freezing point (4.6 ° C), although it is miscible with other solvents, but it still shows insufficient low temperature performance at very low temperatures, as if it still wants to precipitate from the mixture. effect.

PC is a solvent with obvious advantages, high chemical stability, and is not easily decomposed during rectification. It has a boiling point of 242 ° C, a melting point of -48.8 ° C, and a liquid range of up to 290 ° C, which is a very large advantage. It can be used regardless of whether it is hot or cold. It is very rare for solvents. In addition, the solubility of PC is very good, and there are many substances that can be dissolved, and it has excellent versatility. At the same time, the PC is also non-toxic, low-priced, and so on. PC also has a very interesting feature. It has a strong ability to dissolve CO2. It can dissolve 8.5 liters of CO2 per liter of PC at 2.8 atmospheres at 25 ° C, and the solubility increases rapidly when the pressure rises. Therefore, it is used industrially to absorb carbon dioxide in the mixed gas. I have seen a technical solution in the past. In the process of making a soft-pack battery, carbon dioxide is used as a shielding gas. When the electrolyte contains PC, the carbon dioxide is dissolved and absorbed by the PC after the injection, and the internal pressure of the soft-packed battery is lowered. It is tightly attached to the battery core. The idea is to take full advantage of the PC’s ability to dissolve carbon dioxide.
PC has many disadvantages, one of which is that the viscosity is relatively high compared to other solvents, which leads to an electrolyte containing a high PC, although it is less likely to condense at low temperatures, but it is sticky (the actual feeling is not So exaggerated, but this is the case for lithium ion migration), which is not conducive to the migration of lithium ions. The migration of ions cannot keep up with the need, resulting in a large concentration polarization, and the rate performance will be poor. This is also confirmed by experiments. Therefore, generally in the low temperature electrolyte, if it is a small current application, PC can be used, but once the magnification is high, the PC has to carefully control the amount, otherwise the performance is difficult to see.

In the research, people gradually found that in lithium ion batteries, ethylene carbonate (EC) performed better than PC. In addition to the relative dielectric constant (EC 89) is greater than PC (PC 65), it is made into the cycle performance of the battery. It is also better than PC, so EC has slowly developed. For reasons of this reason, the film formation potential of EC on the negative electrode is relatively high. When charging, the potential of the negative electrode is continuously decreased, and the EC with higher reduction potential preferentially precipitates, which participates in the formation of the SEI film, which is advantageous for stabilizing the negative electrode and impedance. Moderate, battery performance is better.

Another advantage of EC is that after dissolution, its viscosity is smaller than PC. For lithium battery electrolytes, a low viscosity means lower ion mobility resistance, which means better battery performance. In addition, there is a hidden reason, that is, the co-embedding side effect of PC on graphite anode materials makes PC not suitable for high concentration use, and EC does not have this limitation. Slow EC replaces PC. It is an essential solvent in the electrolyte and an indispensable component.

But EC is also a problem, and the problem is not small – the melting point is as high as 37 ° C. This is a “class” with the PC. From the structural point of view, PC only has one more methyl group on the ring, but this methyl group brings about molecular asymmetry, which makes the polarity of PC smaller, and it is more difficult to crystallize, so the melting point is greatly reduced.

Among the cyclic carbonates, in addition to EC and PC, there is also a butylene carbonate BC. Since there are two more carbon atoms, BC has two structures, one is one more ethyl than EC, namely 1,2-butanediol cyclic carbonate, or abbreviated as 1,2-BC (CAS 4437-85- 8); The other is two more methyl groups than EC, namely 2,3-butanediol cyclic carbonate, or simply 2,3-BC (CAS 4437-70-1). At present, there are few studies in BC, and samples are not easy to obtain.

In addition, the structure of PC also exists an isomer, namely 1,3-propanediol cyclic carbonate (CAS 2453-03-4), whose molecular structure is a six-membered ring. Generally this compound is not called propylene carbonate (theoretically you can’t get it by propylene and carbonic acid addition), but it is called trimethylene carbonate, or TMC for short. However, the TMC compound seems to be less stable and it is easy to form a polymer. By transesterification of 1,3-propanediol with dmc, TMC can theoretically be obtained, but in fact, TMC polymers are produced. Therefore, the reported method of synthesizing TMC is basically to first manufacture TMC polymer. Depolymerized under certain conditions. However, the TMC compound is relatively friendly to the human body. Many people currently study its application in the medical industry, and rarely see electrolyte research.

Of course, cyclic carbonates are far more than these. There is also a reported carbonate called catechol carbonate, also known as catechol carbonate (abbreviated CC), which is equivalent to eccentricity outside the structure of EC. This compound was obtained on the previous benzene ring and was reported as a lithium electrolyte additive many years ago.

Dimethyl carbonate (DMC) is an environmentally friendly organic synthesis intermediate that can replace highly toxic phosgene and dimethyl sulfate as hydroxylation reagents and methylating agents, and it is also an ideal inclusion. Oxygen gasoline additive.

At present, the synthesis methods of DMC include phosgene method, methanol oxidation hydroxylation method and transesterification method. Among them, the transesterification mower uses cyclohexane to form a cyclic carbonate by carbon dioxide and alkylene oxide, and then transesterifies with methanol to obtain dimethyl carbonate. The method has important industrial application prospects due to simple process, high reaction conversion rate and selectivity, and co-production of glycol.

Propylene carbonate (propylene glycol carbonate) is soluble in water and carbon tetrachloride, mixes with ether, acetone, benzene and other miscible, is a good polar solvent, nature is stable, non-toxic solvent, pure, no corrosion of carbon steel equipment, used for removal of natural gas, petroleum cracking gas, carbon dioxide and hydrogen sulfide in synthetic ammonia feed gas, is an ideal solvent, can also be used as plasticizer, spinning solvent or water solvent dye pigment dispersant, oily solvent and extracting agent of olefins and aromatics. Based on people's concern for resources and environmental problems and the social demand for sustainable development, green chemistry with the goal of eliminating pollution, making rational use of resources and achieving sustainable development has become the hot spot and frontier of current chemistry research. Many processes will be replaced by clean and environmentally friendly processes. The continuous promotion and application of dimethyl carbonate, polycarbonate and polyurethane in its downstream products will inevitably increase the market demand for propylene carbonate.

At present, the most important is used to remove carbon dioxide and hydrogen sulfide from natural gas, oil pyrolysis gas, oil field gas and synthetic ammonia conversion gas.In the electronic industry, it can be used as an excellent medium for high-energy batteries and capacitors, and as a solvent and plasticizer for polymers.

Propylene carbonate can also be used as an oil solvent and as an extraction agent for olefins and aromatics.In the textile industry can be used as synthetic fiber additives and fixatives, spinning solvents or water-solvent dye pigment dispersant; In addition, it is an extremely versatile organic synthesis of raw materials and intermediates.

Linyi Evergreen Chemical Co., Ltd., founded in October 2013, is a wholly-owned subsidiary of ECHEMI group, covering an area of 85 Acres, with a registered capital of 30.5 million yuan, the main production and operation of propylene oxide and other products, propylene carbonate, propylene glycol, dimethyl carbonate and so on.

Evergreen is located in Shandong Linyi Lingang economic development zone, 30 km from lanshan port, 50 km from rizhao port, 100 km from lianyungang port, 120 km from huangdao port. In 2018, Evergreen had passed the work review of enterprise safety production standardization, safety risk hierarchical management and control, and the construction of double prevention system of accident hidden danger investigation and treatment.