CN101357770B - Method for preparing sodium bicarbonate - Google Patents
Method for preparing sodium bicarbonate Download PDFInfo
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- CN101357770B CN101357770B CN2007100123514A CN200710012351A CN101357770B CN 101357770 B CN101357770 B CN 101357770B CN 2007100123514 A CN2007100123514 A CN 2007100123514A CN 200710012351 A CN200710012351 A CN 200710012351A CN 101357770 B CN101357770 B CN 101357770B
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- mother liquor
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Abstract
The invention relates to a method for preparing sodium bicarbonate in the ammonia-soda process, which takes part of heavy alkali separation mother liquor as the component of carbonized supply liquor to carry out carbonization reaction under 15-42 DEG C by a two-stage air inlet mode. The method is characterized in that the heavy alkali separation mother liquor undergoes ammonia absorption, coolingand solid sodium chloride supplementation to form ammonia salt mother liquor; the ammonia salt mother liquor and the stock solution are mixed into half mother liquor as the carbonized supply solutionaccording to a volume ratio of B=3-6; wherein, the total concentration TNH3=5.8-7.3mol/l, the total chlorine concentration Tcl=4.5-5.3mol/l, and the carbonization degree of the carbonization reactionsolution Rc=170-188 percent. The method is characterized by high conversion rate of sodium chloride which is as high as 80-84 percent, low consumption of equipment investment, raw materials and energyandsimple carbonization operation; meanwhile, the method can prepare the heavy alkali crystal with 120-150mum of average grain diameter and uses a centrifuge to separate heavy alkali crystal mush; moreparticularly, the method can avoid a good many disadvantages brought by cooling heavy alkali saturated solution.
Description
Technical field
The present invention relates to a kind of method of producing sodium bicarbonate, particularly in solvay soda process, produce the method for sodium bicarbonate.
Background technology
Japanese kokai publication hei 1-208315 improves traditional solvay soda process of supplying with liquid as carbonization with ammoniated brine.Because the NaCl saturation concentration of ammoniated brine is its total cl concn Tcl (for 4.4-4.5mol/l) and NH
4OH concentration is its total ammonia concentration TNH
3(being 4.8-5.3mol/l) is all low, and degree of carbonisation Rc (30-60%) is lower, and therefore, Tcl (for 4.7-5.0mol/l), the TNH of liquid (weighing up alkali lye down) finished in carburizing reagent
3(for 4.9-5.1mol/l), ammonia chlorine are also all lower than A (T NH3/Tcl is 1.0-1.05), though the degree of carbonisation Rc that goes out alkali lye up to 190% condition under, the transformation efficiency of sodium-chlor has only 73-75%, and the magma concentration at the bottom of the carbonating tower is up to 290-310Kg/m
3The crystallization of sodium bicarbonate quality is also poor, median size only is 80-90 μ m, simultaneously, liquid---the heavy alkali number that ammoniated brine is separated out is many, and thermal discharge is big because the carbonization of carbonization unit volume is supplied with, with the warm eventually just needs of the carburizing reagent that keeps being fit to water cooler is set for removing reaction heat, and refrigerative is heavy alkali saturated solution, so, can bring again water cooler scab easily stifled, need marshalling alternately operating, complicated operation, shortcoming that maintenance capacity is big; The improvement project that Japanese kokai publication hei 1-208315 proposes above-mentioned traditional solvay soda process, with the heavy alkali of part separate mother liquor return with ammoniated brine or pre-carbonization after neutralization of ammonia salt solution mix by the volume ratio of 0.2-1.5, supply with liquid as carbonization after being cooled to 18 ℃ again, under 18-40 ℃, carry out carburizing reagent with two sections intake methods, the Tcl that this improvement project makes this carbonization supply with liquid is 4.6mol/l, TNH
3Be 5.3mol/l, Rc brings up to 93%, thereby, with respect to traditional solvay soda process, to reducing the heavy alkali magma concentration of latter end reaction zone, reduce the generating capacity of nucleus, improve the crystallization of sodium bicarbonate quality, all can make moderate progress heavy alkali amount of separating out and the reaction heat that reduces carbonization unit volume carbonization supply liquid, as reducing the amount of cooling water of reaction heat of carbonization, only need to extract the cooling of part reaction solution out and get final product at the latter end reaction zone installing pump circulation water cooler of carbonating tower, still, by this improvement project, the one, the amount of being blended into that heavy alkali separates mother liquor is few, the 2nd, do not increase the ammonia amount of inhaling, carbonization is supplied with the change of composition of liquid and not obvious, therefore, change to the carburizing reagent condition is also not obvious, by embodiment as seen, even under preferable enforcement environment (ratio of mixture is 0.5), the but still high (190Kg/m of the magma concentration at the bottom of its tower
3), the crystallization of sodium bicarbonate quality does not have tangible improvement, and its median size has only 100 μ m, and the sodium-chlor transformation efficiency does not improve, and separates the NH of mother liquor by its heavy alkali
4Cl/ (NH
4Cl+NaCl) meter also only 74.5%, and in addition, carbonating tower still needs to be provided with water cooler, and refrigerative is still heavy alkali saturated solution, exist in traditional solvay soda process water cooler scab easily stifled, need shortcoming such as marshalling alternately operating still to exist.
Summary of the invention
The object of the present invention is to provide a kind of method of producing sodium bicarbonate, this method is by providing a kind of heavy alkali separation mother liquor that is blended in a large number, can make carburizing reagent in the total ammonia concentration of height, high degree of carbonisation charging, low magma concentration with need not to cool off the carbonization of finishing under the heavy alkali saturated solution condition and supply with liquid, thereby can make that the production of solvay soda process soda ash becomes that a kind of carbonization operation is simple and easy, raw material sodium-chlor utilization ratio height, energy expenditure are low, can make fine soda ash.
Technical solution of the present invention is: a kind of method of producing sodium bicarbonate, separate mother liquor is supplied with liquid as carbonization component with the heavy alkali of part, mode with two sections air inlets under 15-42 ℃ is carried out carburizing reagent, it is characterized in that this heavy alkali separate mother liquor through inhale ammonia, cool off, salt ammonia mother liquor after adding solid sodium chloride and stock liquid by volume B=3-6 be mixed into half mother liquor and supply with liquid as carbonization, its total ammonia concentration TNH
3=5.8-7.3mol/l, total cl concn Tcl=4.5-5.3mol/l, the degree of carbonisation Rc=170-188% of liquid is finished in carburizing reagent.
Described stock liquid B=4-5 by volume is mixed into half mother liquor, the total ammonia concentration of half mother liquor TNH
3=5.9-7.0mol/l, total cl concn Tcl=4.6-5.0mol/l, the degree of carbonisation Rc=176-186% of liquid is finished in carburizing reagent.
The heavy alkali separation mother liquor that the present embodiment is returned is inhaled ammonia earlier, to make TNH
3High ammonia mother liquor, then, because of the mother liquor volume becomes Tcl concentration is fallen greatly in order to remedy to inhale in the ammonia process, in the ammonia mother liquor, add solid salt (NaCl) and become salt ammonia mother liquor, with this salt ammonia mother liquor and stock liquid by volume B=3-6 be mixed into the carbonization that half mother liquor is the present embodiment and supply with liquid, this supplies with liquid and advance CO with two sections under 15-42 ℃ in carbonating tower
2The gas mode is finished carburizing reagent, goes out the heavy alkali of alkali lye after separating heavy alkali and separates mother liquor and return confession this law according to the amount of above-mentioned B value needs and recycle, and remaining removes to distill recovery NH wherein
3And CO
2Can absorb system alkali reaction needed ammonia owing to separate mother liquor suction ammonia more, and in the ammonia mother liquor, can add solid salt to regulate total cl concn, so the inventive method can be supplied with liquid with carbonization with heavy alkali---the TNH of half mother liquor
3Control to 5.8-7.3mol/l, Tcl is adjusted to 4.5-5.3mol/l, therefore, according to system alkali reaction formula, the degree of carbonisation that will go out alkali lye again is controlled in the moderate scope of 170-188%, the Tcl that just can use alkali lye is 4.65-5.45mol/l, and ammonia chlorine is 1.10-1.60 than the A value, just can obtain high sodium-chlor transformation efficiency; In this B value scope, the heavy alkali amount of separating out of unit volume reaction solution and heat of reaction much less in the carbonating tower, so, as long as the heavy alkali unsaturated solution of cooling in advance--half mother liquor, control the inlet temperature of stabilizer (15-22 ℃) of half mother liquor well, these heat of reaction can Remove All by going out the mode of alkali lye with sensible heat fully, and do not need carbonating tower to set up cooling water tank or external cooler to cool off heavy alkali saturated solution, and, at this B value and TNH
3, in the Tcl scope, the degree of carbonisation Rc height of half mother liquor is 135-155%, heavy alkali magma concentration m is low at the bottom of the carbonating tower, is 60-115Kg/m
3, the generating capacity of nucleus is little, therefore can make the crystallization of sodium bicarbonate that particle is thick, separation performance is good.The stock liquid that the present invention uses specifically is meant refined brine (claiming secondary brine again), ammoniated brine, neutralization of ammonia salt solution etc.
When the B value was lower than 3.0, the amount of returning that heavy alkali separates mother liquor was little among the present invention, and the heavy alkali amount of separating out of unit volume reaction solution is big in the carbonating tower, just be difficult to take whole reaction heat of carbonization out of by going out the alkali lye sensible heat, and, owing to need half lower mother liquor inlet temperature of stabilizer of control, less economical on the engineering; When the B value greater than 6.0 the time, can increase the power consumption that liquid is carried in working cycle too much, and make the concentration of free ammonia FNH in ammonia mother liquor and half mother liquor
3With gas concentration lwevel CO
2Ratio be reduced to below 2, will in process of cooling, separate out hydrocarbonate, cause ammonia mother liquor water cooler and half mother liquor water cooler fouling.Increase the suction ammonia amount that heavy alkali separates mother liquor among the present invention, can improve the TNH of half mother liquor
3With the transformation efficiency of sodium-chlor, TNH
3When being lower than 5.8mol/l, the transformation efficiency of sodium-chlor is low; Work as TNH
3When being higher than 7.3mol/l, the free ammonia FNH in all mother liquors of working cycle
3The concentration height, carbonating tower and ammonia absorber tail gas band ammonia are many, the bicarbonate of ammonia (NH in the crystallization of sodium bicarbonate
4HCO
3) content also can increase.The Tcl of the present invention's half mother liquor is lower than 4.5mol/l, and the circulating mother liquor amount is big, also can cause the hydrocarbonate fouling in the water cooler of ammonia mother liquor and half mother liquor; Tcl is higher than 5.3mol/l, is unnecessary for improving the sodium-chlor transformation efficiency, and, need half higher mother liquor inlet temperature of stabilizer of control, what have carbonating tower goes out the too high shortcoming of alkali liquid temperature.The degree of carbonisation Rc that carbonating tower goes out alkali lye among the present invention is higher than at 188% o'clock, requires the height of carbonating tower and carbonization pressure all high, and the time of carburizing reagent is long, and it is big to implement difficulty on the engineering; Rc is lower than at 170% o'clock, needs the high TNH of control
3Concentration also has and above-mentioned TNH
3Identical shortcoming when being higher than 7.3mol/l.
Purpose of the present invention can also reach by following measure: the inventive method is used for solvay soda process and produces when weighing alkali the ratio of mixture B=4-5 of control salt ammonia mother liquor and stock liquid, the total ammonia concentration of half mother liquor TNH
3=5.9-7.0mol/l, total cl concn Tcl=4.6-5.0mol/l goes out alkali lye degree of carbonisation Rc=176-186%, magma concentration m=70-82Kg/m at the bottom of the tower
3Embodiment, this is for obtaining high sodium-chlor transformation efficiency, improve the utilization ratio of raw material sodium-chlor, reduce the still-process energy consumption, and for improving the crystallization of sodium bicarbonate quality, the use whizzer replaces the heavy alkali magma of vacuum filter separation, reduces the calcination process energy consumption, and saving facility investment and minimizing production run expense etc. are all more beneficial.
Heavy alkali separation mother liquor through inhaling ammonia, benefit salt mixes with specified any stock liquid can obtain effect of the present invention.But, when mixing, increased on the flow process and once inhaled ammonia with neutralization of ammonia salt solution.Still will use pre-carbonization system, the circulating mother liquor equivalent is also big, and owing to mixes the CO of later half mother liquor
2Excessive concentration can be brought difficulty to cooling operation, is disadvantageous; Mix also to have how once to inhale ammonia and the big shortcomings of circulating mother liquor equivalent with ammoniated brine; It is best mixing with refined brine, only need once inhale ammonia, does not establish pre-carbonization system, and the circulating mother liquor equivalent is also smaller.
The CO that mentions in the inventive method
2Gas, NH
3, raw materials such as sodium-chlor and refined brine, ammoniated brine, neutralization of ammonia salt solution all are commonly used in the prior art, as the solid sodium chloride of adding, can use washing salt, perhaps use the I and II vacuum refined salt, the sodium-chlor of by-product in the time of also can reclaiming calcium chloride with slops, the purpose that strainer K is set in the scheme is further to remove the contaminant particles that raw material salt is brought into.The present invention can use the C formula tower that proposes among the Chinese patent ZL91106256.4, also can implement in any carbonating tower of not setting up any form water cooler.When the inventive method is used for having now the transformation of solvay soda process soda ash production equipment, do not change technology, equipment and the operation of operations such as crude brine, calcining, distillation, lime.
The inventive method is compared with background technology has following advantage:
1. sodium-chlor transformation efficiency height, can reach 80-84%, on average improve 8%, by salt consumption 1500kg/t, but the about 120kg/t of conservation sodium-chlor, and heavy in a large number alkali separates mother liquor and turns back to the stock liquid system, has reduced the filtration of bicarbonate loss, by filter loss soda ash 16kg/t, can reduce soda ash product loss 13kg/t, distillation mother liquor equivalent is little, can also reduce the low-pressure steam consumption of distillation process.
2. the crystallization of sodium bicarbonate quality is good, crystalline particle big (＞120 μ m), during as use C formula tower, median size can reach 150 μ m, and epigranular, separation and scourability are good, can adopt whizzer to replace vacuum filter to separate heavy alkali magma, and filter cake moisture content can be reduced to below 12% by 18-20%, significantly reduce the middle pressure steam consumption of calcination process, and quality of soda ash is good, and salt is lower than 0.4%, and loose density can reach 600kg/m
3, have good packing and use properties.
3. pre-carbonating tower system is not established in carbonating tower carbon steel manufacturing, and carburizing reagent can be finished in a step, and the temperature rise of inhaling ammonia is little, and the concentration of free ammonia of ammonia mother liquor is low, can replace tall and big ammonia absorption tower by enough small and exquisite injection ammonia absorbers, significantly save the facility investment expense, day-to-day maintenance is also low.
4. carbonating tower is arranged in the open, also need not establish water tank maintenance framework, and the whizzer factory building is shorter than vacuum filtration factory building, spray ammonia absorber factory building need not be set separately, therefore, it is short much smaller that (ammonia) factory building is inhaled in carbon (change) filter (mistake) and steaming (heating up in a steamer), and the civil engineering investment can obviously reduce.
5. carbonating tower is not established the heavy alkali saturated solution of water cooler cooling, and it is light to scab, and working cycle is long, need not organize into groups and carry out frequent tower or switch outer cooler crop rotation cleaning; Regular job need not be carried out meticulous chilled water modulation, also the precise dose Controlling System needn't be set, and operates very simply, realizes operation automation easily.
6. the investment that is used for existing solvay soda process soda ash production equipment transformation more economizes, and it is faster to take effect.
As seen from above-mentioned: the present invention has solved since nearly a century and a half that the sodium-chlor transformation efficiency is low the production of solvay soda process soda ash, crystallization of sodium bicarbonate is of poor quality, the carbonating tower complicated operation, water cooler scabs easily stifled and need technical barrier such as many grouping operations.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
As shown in the figure, salt ammonia mother liquor 13 is mixed in proportion into half mother liquor 1 with refined brine 14 in mixing tank I, after water cooler J cooling and strainer K purification, deliver to the top of carbonating tower D again, feed lime-kiln gas 3 and feed calciner gas 2 at the tower middle part respectively and carry out carbonating in the tower bottom, finish the crystallization of sodium bicarbonate precipitation process, carbonization tail gas 5 discharges exhaust gas purification system from cat head, going out alkali lye (heavy alkali magma) 4 washs into heavy alkali 6 and separates mother liquor 8 with adding wash water 7 through whizzer E separation, heavy alkali 6 send calcination process, separates the small portion 8 of mother liquor 8
1Go distillation process ammonia still process, major part send ammonia absorber F to absorb the ammonia gas mixture 9 of ammonia still, add the ammonia 10 that process consumes simultaneously, ammonia mother liquor 11 removes to mend salt device H and adds solid sodium chloride 12 and become salt ammonia mother liquor 13 after water cooler G cooling, be mixed into half mother liquor 1 then in mixing tank I with from the refined brine 14 of salt solution operation, so the present invention is implemented in circulation.
Embodiment 1
Heavy alkali separates mother liquor (component: TNH
36.48mol/l, Tcl4.83mol/l, CO
21.81mol/l) ammonification 1.63mol/l and the salt ammonia mother liquor (component: TNH of adding solid salt 0.21mol/l
37.70mol/l, Tcl4.75mol/l, CO
21.89mol/l) 24.5m
3/ h and refined brine (component: TNH
30.60mol/l, Tcl5.25mol/l, CO
20.24mol/l) 4.9m
3/ h is mixed into half mother liquor by ratio of mixture B=5, its composition: TNH
36.52mol/l, Tcl4.83mol/l, CO
21.61mol/l degree of carbonisation Rc is 148%, it is cooled to 20 ℃ of adding φ 1600mm C formula towers carries out carbonization, sodium bicarbonate magma concentration 75Kg/m at the bottom of the tower
3, go out 38.6 ℃ of alkali liquid temperatures, degree of carbonisation Rc182%, component: C NH
3(NH4Cl) 4.18mol/l, Tcl4.95mol/l, CO
21.85mol/l ammonia chlorine is 1.34 than A.The sodium-chlor transformation efficiency is 84.4%.Crystallization of sodium bicarbonate median size 159 μ m, it is spherical and cylindrical that its shape mostly is, and size ratio is more even, and the isolating heavy buck of whizzer divides 9.5%, soda ash salinity 0.32%.Carbonization tail gas contains CO
25.3%, band NH
37.0g/Nm
3Go the heavy alkali of distillatory to separate mother liquor equivalent 4.89m
3/ t.
Embodiment 2
Heavy alkali separates mother liquor ammonification 2.34mol/l, and the salt ammonia mother liquor of mending salt 0.31mol/l is mixed into half mother liquor by B=3 and refined brine, component: TNH
36.01mol/l, Tcl4.97mol/l, CO
21.30mol/l Rc137% is cooled to 15.0 ℃ with it and adds the bamboo rain-hat tower that φ 1200mm do not establish cooling water tank and carry out carbonization, magma concentration 107Kg/m at the bottom of the tower
3, go out 41.8 ℃ of alkali liquid temperatures, Rc186%, component: CNH
34.20mol/l, Tcl5.15mol/l, CO
21.55mol/l ammonia chlorine is 1.20 than A.The sodium-chlor transformation efficiency is 81.4%.Crystallization of sodium bicarbonate median size 122 μ m, refined brine equivalent 4.00m
3/ t, distillation mother liquor equivalent 4.91m
3/ t.
Embodiment 3
Salt ammonia mother liquor and refined brine that heavy alkali separates mother liquor ammonification 1.64mol/l and benefit salt 0.18mol/l are mixed into half mother liquor by B=6, its component: TNH
37.33mol/l, Tcl4.55mol/l, CO
22.08mol/l Rc141% is cooled to 22 ℃ of adding φ 160mm C formula towers and carries out carbonization, magma concentration 64Kg/m at the bottom of the tower
3, go out 39.4 ℃ of alkali liquid temperatures, Rc170%, component: CNH
33.94mol/l, Tcl4.65mol/l, CO
22.39mol/l A is 1.60.The sodium-chlor transformation efficiency is 84.5%, crystallization of sodium bicarbonate median size 127 μ m.Refined brine equivalent 3.76m
3/ t, distillation mother liquor equivalent 5.21m
3/ t.
Claims (2)
1. method of producing sodium bicarbonate, separate mother liquor is supplied with liquid as carbonization component with the heavy alkali of part, mode with two sections air inlets under 15-42 ℃ is carried out carburizing reagent, it is characterized in that this heavy alkali separate mother liquor through inhale ammonia, cool off, salt ammonia mother liquor after adding solid sodium chloride and stock liquid by volume B=3-6 be mixed into half mother liquor and supply with liquid as carbonization, its total ammonia concentration TNH
3=5.8-7.3mol/L, total cl concn TCl=4.5-5.3mol/L, the degree of carbonisation Rc=170-188% of liquid is finished in carburizing reagent, and described stock liquid is refined brine, ammoniated brine.
2. the method for producing sodium bicarbonate according to claim 1, it is characterized in that described stock liquid by volume B=4-5 be mixed into half mother liquor, the total ammonia concentration of half mother liquor TNH
3=5.9-7.0mol/L, total cl concn TCl=4.6-5.0mol/L, the degree of carbonisation Rc=176-186% of liquid is finished in carburizing reagent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100123514A CN101357770B (en) | 2007-07-30 | 2007-07-30 | Method for preparing sodium bicarbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100123514A CN101357770B (en) | 2007-07-30 | 2007-07-30 | Method for preparing sodium bicarbonate |
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| Publication Number | Publication Date |
|---|---|
| CN101357770A CN101357770A (en) | 2009-02-04 |
| CN101357770B true CN101357770B (en) | 2010-04-21 |
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| CN2007100123514A Expired - Fee Related CN101357770B (en) | 2007-07-30 | 2007-07-30 | Method for preparing sodium bicarbonate |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803587B (en) * | 2013-12-23 | 2015-06-10 | 河北工业大学 | Method for preparing sodium carbonate through wastewater discharge-free ammonia circulation |
| CN108439434B (en) * | 2018-03-07 | 2023-04-25 | 武汉德泽环保科技有限公司 | Method and device for producing baking soda |
| CN111960442B (en) * | 2020-08-31 | 2022-12-30 | 天津渤化永利化工股份有限公司 | Automatic control method for combined alkali ammonia absorption |
| CN112758959A (en) * | 2021-03-12 | 2021-05-07 | 自贡鸿鹤制药有限责任公司 | Preparation method of sodium bicarbonate |
| CN114408949B (en) * | 2022-01-26 | 2023-09-22 | 江苏苏盐井神股份有限公司 | Low-salt or ultra-low-salt sodium carbonate production process and device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103005A (en) * | 1987-04-28 | 1987-12-30 | 自贡市鸿鹤化工总厂 | Carbonization tower cooled externally by natural circulation |
| CN1059883A (en) * | 1991-10-05 | 1992-04-01 | 化工部制碱工业研究所 | Produce the method and apparatus of sodium bicarbonate |
| CN1075935A (en) * | 1993-01-20 | 1993-09-08 | 王全 | Produce the method for sodium bicarbonate |
| CN2868987Y (en) * | 2006-08-14 | 2007-02-14 | 河南金山化工有限责任公司 | Carbonizing tower for preparing sodium hydrogen carbonate |
-
2007
- 2007-07-30 CN CN2007100123514A patent/CN101357770B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103005A (en) * | 1987-04-28 | 1987-12-30 | 自贡市鸿鹤化工总厂 | Carbonization tower cooled externally by natural circulation |
| CN1059883A (en) * | 1991-10-05 | 1992-04-01 | 化工部制碱工业研究所 | Produce the method and apparatus of sodium bicarbonate |
| CN1075935A (en) * | 1993-01-20 | 1993-09-08 | 王全 | Produce the method for sodium bicarbonate |
| CN2868987Y (en) * | 2006-08-14 | 2007-02-14 | 河南金山化工有限责任公司 | Carbonizing tower for preparing sodium hydrogen carbonate |
Non-Patent Citations (2)
| Title |
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| 王全.环流式碳化塔研究与操作实践(二)重碱结晶过程模试.纯碱工业 1.2003,(1),3-10. |
| 王全.环流式碳化塔研究与操作实践(二)重碱结晶过程模试.纯碱工业 1.2003,(1),3-10. * |
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Address after: 116023, room 1, building 11, 701 Nishimura street, Shahekou District, Liaoning, Dalian Patentee after: Wang Quan Address before: 116023, room 23, 201 Haizhou street, Shahekou District, Liaoning, Dalian Patentee before: Wang Quan |
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