CN1206165C - Preparation of chromium anhydride - Google Patents
Preparation of chromium anhydride Download PDFInfo
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- CN1206165C CN1206165C CN 03111708 CN03111708A CN1206165C CN 1206165 C CN1206165 C CN 1206165C CN 03111708 CN03111708 CN 03111708 CN 03111708 A CN03111708 A CN 03111708A CN 1206165 C CN1206165 C CN 1206165C
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- China
- Prior art keywords
- chromic trioxide
- solution
- preparation
- temperature
- chromic
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000009834 vaporization Methods 0.000 claims description 17
- 230000008016 vaporization Effects 0.000 claims description 17
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 2
- 230000001684 chronic effect Effects 0.000 abstract 2
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 19
- 239000011651 chromium Substances 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 2
- CLYBIZZUYVGGKO-UHFFFAOYSA-L Cl[Cr](=O)(=O)O[Cr](Cl)(=O)=O Chemical compound Cl[Cr](=O)(=O)O[Cr](Cl)(=O)=O CLYBIZZUYVGGKO-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a method for preparing chronic anhydride, which comprises the following steps: a concentrated sulfuric acid solution and a sodium dichromate dihydrate solution are fed into a reactor, mixed to react according to the mol ratio of 1.8 to 2.4, vaporized under the reduced pressure in the vacuum state until chromic anhydride crystals are separated, dewatered, washed by a chromic anhydride solution and finally dried so as to form the chronic anhydride. The concentration of the sodium dichromate dihydrate solution is preferably 65 to 75%, the mixing reaction is carried out by stirring for 2 to 3 hours, the evaporation temperature is 105 to 125DEG C, the dewatering step adopts the centrifugal separation mode, the dewatering temperature is 80 to 95DEG C, the chromic anhydride solution is preferably the saturated chromic anhydride solution, the temperature of the chromic anhydride solution is 85 to 95DEG C, the drying temperature is 100 to 105DEG C, and the drying time is 2 to 3 hours.
Description
Technical field
The present invention relates to Inorganic Chemicals, relate to a kind of preparation method of chromic trioxide more specifically.
Background technology
Chromic trioxide is one of main products of chromic salts series in the inorganic salt, it is important Inorganic Chemicals, be widely used in plating, metal passivation, manufacturing chemical fertilizer with industries such as catalyzer, medicine, chrome yellow, chromoxide green and mordants, in national economy, play an important role.
At present, countries in the world manufacture chromic trioxide is raw material with the sodium dichromate all, and production technique has crystallization process, electrolytic process and scorification.Crystallization process belongs to cleaning procedure, be the state-of-the-art production method of generally acknowledging in the world, but this technology has only Britain a company to have, and its technical scheme is unexposed so far.Electrolytic process also belongs to cleaning procedure, have only external two chromium salt factory to use at present, but because current consumption is too big, the cost height is difficult to be accepted by other producers.The method that now comprises China's production chromic trioxide in the world is scorification, the weak point of scorification is: a. reaction process temperature height, not only there are the chromium of containing water vapor and hydrogenchloride to overflow, but also because the reddish-brown gas chlorination of the participation of the impurity sodium-chlor in sodium dichromate reaction generation severe toxicity is chromyl, the corrosion production equipment, the infringement workers ' health, contaminate environment.B. owing to the later stage (comprising clarification, layering, separation) of reaction process, temperature of charge (200 ℃) is higher than the decomposition temperature (190 ℃) of chromic acid, causes chromic trioxide to be decomposed into Cr
3+, and, both reduced yield (being generally 92%) with temperature rising aggravation, and influenced quality again, cause the quality product heterogeneity.C. the by product sodium pyrosulfate contains quite high water-soluble Cr
3+And water-insoluble, be difficult to comprehensive utilization, even when it is back to the neutralization of Sodium chromate or acidifying, produce new chromium residue again, can only store up, in addition, the sodium pyrosulfate quantity discharged is big, has increased the weight of environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of non-environmental-pollution, cost is low, yield is high and the by product sodium pyrosulfate does not contain water-soluble Cr
3+Preparation method with the chromic trioxide of water-insoluble.
Purpose of the present invention can realize by following technical measures:
This preparation method at first send the reactor hybrid reaction with the vitriol oil and sodium dichromate solution by 1.8～2.4 mol ratios, the back is that reduction vaporization to chromic trioxide crystal is separated out under 370～500mmHg state in vacuum tightness, use the chromic trioxide solution washing again after dewatering, last drying forms.
Purpose of the present invention also can realize by following technical measures:
The concentration of sodium dichromate solution is 65～75%, the vitriol oil and sodium dichromate solution are by the preparation of 2.1～2.2 mol ratios, described hybrid reaction is under agitation to react 2～3 hours, vaporization temperature is 105～125 ℃, and the centrifugation mode is adopted in described dehydration, and described dehydration temperaturre is 80～95 ℃, described chromic trioxide solution is saturated chromic trioxide solution, described chromic trioxide solution temperature is 85～95 ℃, and described bake out temperature is 100～105 ℃, and drying time is 2～3 hours.
The present invention CI that reduction vaporization produced under vacuum state
2, HCI, CrO
2CI
2Gas send buck to absorb, and contains chromium NaHSO after the centrifugation
4Solution is directly used in neutralization or acidifying, and the washing lotion behind the chromic trioxide solution washing is sent the reduction vaporization operation.Do not decompose in order to ensure chromic trioxide, guarantee quality product and can will contain the chromium gas recovery, adopt and under vacuum state, evaporate.The height of vaporization temperature is decided on the size of vacuum tightness, and when vacuum tightness was big, vaporization temperature was low; When vacuum tightness hour, the vaporization temperature height.Usually select and the corresponding vaporization temperature of vacuum tightness according to the viscosity of evaporating solns, when general vacuum tightness was 370～500mmHg, corresponding terminal temperature was 120～125 ℃.The vitriol oil and sodium dichromate solution generate chromic trioxide (CrO in the reactor hybrid reaction
3) and sodium pyrosulfate (NaHSO
4) mixing liquid, the moisture content in the reduction vaporization liquid makes most of CrO in the solution
3Crystallization makes NaHSO simultaneously
4Concentration near but be lower than NaHSO
4The concentration that crystal begins to form is isolated crystal CrO again from solution
3, because NaHSO
4Mainly be present in CrO
3Plane of crystal is purified with saturated chromic trioxide solution washing, and drying promptly gets granular chromic trioxide goods again.These goods contain chromic trioxide 〉=99.90%, contain water-insoluble≤0.005%, and the sulfur-bearing hydrochlorate is (with SO
4 2-Meter)≤0.005%, contain sodium≤0.01%.
The present invention is because the slurries after the evaporation contain crystallization CrO
3With dissolved NaHSO
4, for preventing NaHSO
4Separate out, separation temperature generally is controlled at more than 85 ℃ to well.In order to ensure the least possible dissolving of chromic trioxide particle, improve productive rate, the temperature of the near saturated chromic trioxide solution that adopts during washing generally is controlled at the filter cake temperature basic identical.
Temperature of reaction of the present invention is low also carries out in the aqueous solution all the time, and reaction and evaporation are all carried out in decompression and air tight condition, do not produce chlorochromic anhydride, and it is all recyclable to contain chromium droplet and hydrogenchloride, non-environmental-pollution; Chromic trioxide in the preparation process does not decompose, the yield height, and the product purity height, the quality homogeneous, the granular crystal liquid flowability is good; The by-product sodium pyrosulfate does not contain water-soluble Cr
3+And water-insoluble, can directly return preceding operation, replace sulfuric acid to be used for the Sodium chromate acidifying; Technology is simple, and cost is low.
Embodiment
Embodiment 1: earlier be that 95% the vitriol oil and concentration are that 70% sodium dichromate solution joins in the reactor by 2.2 mol ratios with concentration, heater voltage be 170V and stir at a slow speed under hybrid reaction 2 hours, after afterwards reduction vaporization (the control vaporization temperature is 120 ℃) is separated out to chromic trioxide crystal major part under vacuum state, utilize whizzer under 85 ℃ of temperature controls, to dry again, filter cake is 87 ℃ chromic trioxide solution washing with nearly saturated temperature, dried 3 hours down at 102 ℃ at last, pack behind the naturally cooling.
Embodiment 2: earlier be that 96% the vitriol oil and concentration are that 72% sodium dichromate solution joins in the reactor by 2.1 mol ratios with concentration, heater voltage be 170V and stir at a slow speed under hybrid reaction 3 hours, after afterwards reduction vaporization (the control vaporization temperature is 110 ℃) is separated out to chromic trioxide crystal major part under vacuum state, utilize whizzer under 90 ℃ of temperature controls, to dry again, filter cake is 92 ℃ chromic trioxide solution washing with saturated temperature, dried 2 hours down at 105 ℃ at last, pack behind the naturally cooling.
Among embodiment 1 and the embodiment 2, through the CI that reduction vaporization produced
2, HCI, CrO
2CI
2Gas send buck to absorb, and contains chromium NaHSO under whizzer gets rid of
4Filtrate is directly used in neutralization or acidifying, and the washing lotion behind the chromic trioxide solution washing is sent the reduction vaporization operation.
The present invention can implement arbitrarily in affiliated technical field.
Claims (10)
1, a kind of preparation method of chromic trioxide, it is characterized in that: send the reactor hybrid reaction with the vitriol oil and sodium dichromate solution by 1.8～2.4 mol ratios earlier, the back is that reduction vaporization to chromic trioxide crystal is separated out under 370～500mmHg state in vacuum tightness, use the chromic trioxide solution washing again after dewatering, last drying forms.
2, the preparation method of a kind of chromic trioxide according to claim 1, the concentration that it is characterized in that sodium dichromate solution is 65～75%.
3, the preparation method of a kind of chromic trioxide according to claim 1 is characterized in that the vitriol oil and sodium dichromate solution prepares by 2.1～2.2 mol ratios.
4, the preparation method of a kind of chromic trioxide according to claim 1 is characterized in that described hybrid reaction is under agitation to react 2～3 hours.
5, the preparation method of a kind of chromic trioxide according to claim 1 is characterized in that vaporization temperature is 105～125 ℃.
6, the preparation method of a kind of chromic trioxide according to claim 1 is characterized in that described dehydration selects the centrifugation mode for use.
7, the preparation method of a kind of chromic trioxide according to claim 5 is characterized in that described dehydration temperaturre is 80～95 ℃.
8, the preparation method of a kind of chromic trioxide according to claim 1 is characterized in that described chromic trioxide solution is saturated chromic trioxide solution.
9, the preparation method of a kind of chromic trioxide according to claim 7 is characterized in that described chromic trioxide solution temperature is 85～95 ℃.
10, the preparation method of a kind of chromic trioxide according to claim 1 is characterized in that described bake out temperature is 100～105 ℃, and drying time is 2～3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111708 CN1206165C (en) | 2003-01-09 | 2003-01-09 | Preparation of chromium anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111708 CN1206165C (en) | 2003-01-09 | 2003-01-09 | Preparation of chromium anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424258A CN1424258A (en) | 2003-06-18 |
| CN1206165C true CN1206165C (en) | 2005-06-15 |
Family
ID=4790146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03111708 Expired - Fee Related CN1206165C (en) | 2003-01-09 | 2003-01-09 | Preparation of chromium anhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1206165C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020316B (en) * | 2010-12-29 | 2013-03-27 | 中国科学院过程工程研究所 | Method for preparing chromic anhydride from potassium chromate |
| CN104495931B (en) * | 2014-12-22 | 2017-09-26 | 中国科学院过程工程研究所 | A kind of potassium chromate liquid phase reactor crystallizes the production method of chromic anhybride |
| CN106277053B (en) * | 2016-07-25 | 2019-01-08 | 中国科学院过程工程研究所 | A kind of preparation method of chromium oxide |
| CN112429776B (en) * | 2020-12-07 | 2023-07-14 | 乔柏人 | Process for producing chromic anhydride and ferrous oxalate by taking ferrochrome as raw material |
-
2003
- 2003-01-09 CN CN 03111708 patent/CN1206165C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1424258A (en) | 2003-06-18 |
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Effective date of registration: 20090227 Address after: No. five Liu Liu gate 14, Ji'nan, Shandong Patentee after: Yuxing Chemical Co., Ltd., Jinan Address before: No. five Liu Liu gate 14, Ji'nan, Shandong Patentee before: Yuxing Chemical General Plant, Jinan |
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