CN115536491A - Production method for producing trimethylolpropane by recycling carbide slag - Google Patents
Production method for producing trimethylolpropane by recycling carbide slag Download PDFInfo
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- CN115536491A CN115536491A CN202211214360.2A CN202211214360A CN115536491A CN 115536491 A CN115536491 A CN 115536491A CN 202211214360 A CN202211214360 A CN 202211214360A CN 115536491 A CN115536491 A CN 115536491A
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- carbide slag
- formaldehyde
- trimethylolpropane
- agent
- recycling
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- 239000002893 slag Substances 0.000 title claims abstract description 86
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 97
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006482 condensation reaction Methods 0.000 claims abstract description 25
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 22
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 21
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims description 34
- 239000013078 crystal Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 27
- 239000012752 auxiliary agent Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 alkali metal molybdate Chemical class 0.000 claims description 21
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 20
- 229920002401 polyacrylamide Polymers 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000008098 formaldehyde solution Substances 0.000 claims description 16
- 238000007792 addition Methods 0.000 claims description 15
- 239000008394 flocculating agent Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 13
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 abstract description 12
- 229940044172 calcium formate Drugs 0.000 abstract description 12
- 239000004281 calcium formate Substances 0.000 abstract description 12
- 235000019255 calcium formate Nutrition 0.000 abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 abstract description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000007323 disproportionation reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000012716 precipitator Substances 0.000 description 7
- 239000005997 Calcium carbide Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 150000001342 alkaline earth metals Chemical group 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a production method for producing trimethylolpropane by recycling carbide slag, which is characterized in that calcium hydroxide solution prepared from carbide slag produced by PVC (polyvinyl chloride) preparation by an acetylene method is used as a catalyst and added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials. The method utilizes a large amount of calcium hydroxide solid waste carbide slag generated in PVC production by an acetylene method as a catalyst of a disproportionation method, solves the problem that the carbide slag is greatly floated by the quality of raw material carbide and process conditions, and has the difficulties of high impurity content, complex impurity types, slag removal of the carbide slag and difficult effective separation from products. Meanwhile, the wall-bonding phenomenon generated by calcium formate is easily caused by directly adding a calcium hydroxide solution as a catalyst, and the solid formed by calcium formate wall-bonding has the characteristics of strong adhesive force and compact solid, is difficult to clean, high in finished product, easy to cause equipment blockage and stop, and can not be cleaned and discarded in serious cases.
Description
Technical Field
The invention belongs to the field of chemical production, and particularly relates to a production method for producing trimethylolpropane by recycling carbide slag.
Background
Acetylene prepared by a calcium carbide method generates a large amount of calcium carbide slag waste, the calcium carbide slag waste mainly contains calcium hydroxide, impurities mainly comprise a plurality of metal oxides such as silicon, aluminum and the like, the calcium carbide slag is greatly floated when being subjected to the quality of raw calcium carbide and process working conditions, and the calcium carbide slag is high in impurity content, complex in impurity types, difficult in slag removal and difficult to effectively separate from products. In the separation of calcium formate, the wall-bonding phenomenon of calcium formate is easy to occur, and the situations of pipe blockage and too thick wall-hanging on the inner wall of equipment are easy to cause.
Disclosure of Invention
In order to solve the technical problem, the invention provides a production method for producing trimethylolpropane by recycling carbide slag.
The technical scheme adopted by the invention is as follows:
a production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding anti-saccharification auxiliary agent and deionized water into formaldehyde solution, then adding carbide slag and n-butyl aldehyde according to reaction
Uniformly adding the mixture for condensation reaction at the reaction temperature of 25-47 ℃ within 100-120 minutes;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystallization particles to be uniform and crystallization time to tend to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by the secondary filtration, and collecting and treating the filter residue obtained by the secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is completed.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is (0.2 to 0.5): 1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is (0.5-3): 1, the molar ratio of formaldehyde to n-butyraldehyde is (1-5): 1.
preferably, in the step S1, the calcium hydroxide in the carbide slag is 60 to 70% by mass.
Further preferably, in the step S1, the concentration of the formaldehyde solution is 90-150g/L.
Further preferably, in the step S2, the crystal form finishing agent is a compound organic silicon series.
More preferably, in the step S2, the composite type organosilicon is polydimethylsiloxane or Cyclic (CH) 3 ) 10 Si 5 O 5 Or linear (CH) 3 ) 12 Si 5 O 4 Or a combination thereof.
Further preferably, in the step S3, the flocculating agent is a compound polyacrylamide precipitating agent added with an aluminum agent.
Further preferably, in the step S3, the molecular weight of the polymer containing aluminum chloride or cationic polymer is 1200-180
The molecular weight of ten thousand units of PAM or nonionic is 2000 ten thousand units of PAM or a combination thereof.
The compound polyacrylamide aluminum-added precipitator is used for accelerating the precipitation effect, particularly for large particles of carbide slag.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is one or a mixture of any one of alkali metal molybdate, alkaline earth metal molybdate, alkali metal tungstate and manganese salt, and the dosage of the formose inhibitor is 1-10ppm of the mass of formaldehyde.
The invention has the beneficial effects that:
1. the invention utilizes a large amount of calcium hydroxide solid waste carbide slag generated in the production of PVC by an acetylene method, and reuses the solid waste.
2. The company utilizes a large amount of calcium hydroxide solid waste carbide slag generated in PVC production by an acetylene method as a catalyst of a disproportionation method, solves the wall bonding phenomenon generated by calcium hydroxide as a catalyst to separate calcium formate, and the solid formed by calcium formate wall bonding has the characteristics of strong adhesive force and compact solid, is difficult to clean, is high in finished product, is easy to cause equipment blockage and parking, and can not be cleaned and discarded in severe cases.
3. The addition of the saccharification inhibitor can completely inhibit the occurrence of the saccharification of the formaldehyde, so that the disproportionation reaction is smoothly carried out.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a comparison of the situation of wall hanging on the inner wall of a calcium formate bottle without and with the addition of the auxiliary agent;
FIG. 3 is a graph of the settling time of the invention without the addition of flocculant;
FIG. 4 is a comparison of the addition of an aluminum-containing precipitant in accordance with the present invention with an anionic polyacrylamide precipitant;
wherein: a size mixing tank 1, a condensation kettle 2, a precipitation filtering device 3, a secondary filtering device 4, a slag filling hopper 5 and a filtrate tank 6.
Detailed Description
The technical solutions of the present invention will be described in detail below with reference to the accompanying drawings and specific examples, but the present invention should not be construed as being limited to the implementable scope of the present invention.
In the following examples, the carbide slag is produced by preparing PVC carbide from acetylene, and the carbide comprises, by mass, 63.93% of calcium oxide, 1.27% of magnesium oxide, 0.50% of aluminum oxide, 0.96% of ferric oxide, 7.90% of silicon dioxide, and 25.44% of loss on ignition. The carbide slag has a specific gravity of 1.82 and a dry volume weight of 0.683 g/cm 3 Wet volume weight of 1.366 g/cm 3 The screen residue of the fineness passing through a 4900-hole sieve per square centimeter is 14.4 percent.
Example 1
A production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding anti-saccharification auxiliary agent and deionized water into formaldehyde solution, then adding carbide slag and n-butyl aldehyde according to reaction
Uniformly adding the mixture for condensation reaction at the reaction temperature of 30 ℃ within 100-120 minutes;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystal particles to be uniform and enabling the crystallization time to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by secondary filtration, and collecting and treating the filter residue obtained by secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is 0.3:1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is 0.4:1, the molar ratio of formaldehyde to n-butyraldehyde is 4:1.
further preferably, in the step S1, the concentration of the formaldehyde solution is 100g/L.
Further preferably, in the step S2, the crystal form finishing agent is a compound type organic silicon series, and the crystal form finishing agent is polydimethylsiloxane.
Further preferably, in step S3, in order to accelerate the precipitation effect, especially large particles of the carbide slag, the flocculant is a compound polyacrylamide type aluminum-added precipitator.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is alkaline earth metal molybdate, and the alkaline earth metal molybdate is manganese molybdate, and the amount of the alkaline earth metal molybdate is 6ppm of the mass of formaldehyde.
Step S1, adding an anti-saccharification auxiliary agent, step S2, adding a crystal form finishing agent, step S3, a flocculating agent (experimental conditions of example 1), and comparing with no addition of an auxiliary agent: and (3) adding no anti-saccharification auxiliary agent in the step S1, no crystal form finishing agent in the step S2, no flocculating agent in the step S3, and comparing the two conditions of wall hanging of the inner wall of the calcium formate bottle added with the auxiliary agent.
As shown in fig. 2, fig. 2a shows that calcium formate is obviously attached to the inner wall of the bottle after the condensation liquid is poured out without adding the auxiliary agent; FIG. 2b shows that the adhesion of calcium formate to the inner wall of the bottle was improved significantly after the addition of the auxiliary (conditions of example 1), and that the slight adhesion of calcium formate to the inner wall of the mouth was caused by the rapid cooling of the upper part and the lower part of the liquid surface during pouring and the rapid cooling of the calcium formate and trimethylolpropane.
Example 2
A production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding anti-saccharification auxiliary agent and deionized water into formaldehyde solution, then adding carbide slag and n-butyl aldehyde according to reaction
Uniformly adding the mixture for condensation reaction at the reaction temperature of 30 ℃ within 100-120 minutes;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystal particles to be uniform and enabling the crystallization time to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by secondary filtration, and collecting and treating the filter residue obtained by secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is 0.3:1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is 0.4:1, the molar ratio of formaldehyde to n-butyraldehyde is 3:1. in the step S1, the mass percentage of the calcium hydroxide in the carbide slag is 65%.
Further preferably, in the step S1, the concentration of the formaldehyde solution is 120g/L.
Further preferably, in the step S2, the crystal form finishing agent is a composite organosilicon series, and is polydimethylsiloxane.
Further preferably, in step S3, in order to accelerate the precipitation effect, especially large particles of the carbide slag, the flocculant is a compound polyacrylamide type aluminum-added precipitator, and the polyaluminium chloride is compounded with cationic PAM with a molecular weight of 180 ten thousand units according to a mass ratio of 1:3.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is alkaline earth metal molybdate, and the alkaline earth metal molybdate is manganese molybdate, and the amount of the alkaline earth metal molybdate is 6ppm of the mass of formaldehyde.
And S1, adding the anti-saccharification auxiliary agent, and comparing the impurity content in the primary trimethylolpropane distillate without adding the anti-saccharification auxiliary agent.
TABLE 1
As can be seen from Table 1, under the same conditions, the content of impurities in the final trimethylolpropane product is reduced by 5.3% when the anti-saccharification auxiliary agent is added or not added, which is obviously helpful for inhibiting the generation of impurities.
Example 3
A production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding anti-saccharification auxiliary agent and deionized water into formaldehyde solution, then adding carbide slag and n-butyl aldehyde according to reaction
Uniformly adding the mixture for condensation reaction at the reaction temperature of 30 ℃ within 100-120 minutes;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystal particles to be uniform and enabling the crystallization time to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by secondary filtration, and collecting and treating the filter residue obtained by secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
In the step S1, the mass percentage of the calcium hydroxide in the carbide slag is 65%.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is 0.3:1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is (0.4): 1, the molar ratio of formaldehyde to n-butyraldehyde is 3:1.
further preferably, in the step S1, the concentration of the formaldehyde solution is 120g/L.
Further preferably, in the step S2, the crystal form finishing agent is a compound organic silicon series, and the crystal form finishing agent is a Cyclic (CH) 3 ) 10 Si 5 O 5 。
Further preferably, in step S3, in order to accelerate the precipitation effect of the flocculant, especially large particles of the carbide slag, a compound polyacrylamide type aluminum-adding precipitator is used, and polyaluminium chloride and non-ionic PAM with a molecular weight of 2000 ten thousand units are compounded according to a mass ratio of 1:2.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is alkaline earth metal molybdate, and the alkaline earth metal molybdate is manganese molybdate, and the amount of the alkaline earth metal molybdate is 6ppm of the mass of formaldehyde.
And (3) comparing the effect of adding no flocculant and the effect of adding flocculant for precipitation for 2 minutes in the step S3.
As shown in FIG. 3, FIG. 3a shows that the solution is turbid, the precipitation effect is poor and the solution is not layered for a long time without adding a flocculating agent; FIG. 3b shows that after the flocculant is added, the solution is quickly layered in a short time, and the supernatant is clear and transparent, so that the effect is obvious.
Example 4
A production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding anti-saccharification auxiliary agent and deionized water into formaldehyde solution, then adding carbide slag and n-butyl aldehyde according to reaction
Uniformly adding the mixture for condensation reaction at the reaction temperature of 30 ℃ within 100-120 minutes;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystal particles to be uniform and enabling the crystallization time to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by secondary filtration, and collecting and treating the filter residue obtained by secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is 0.3:1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is 0.4:1, the molar ratio of formaldehyde to n-butyraldehyde is 3:1.
in the step S1, the mass percentage of the calcium hydroxide in the carbide slag is 65%.
Further preferably, in the step S1, the concentration of the formaldehyde solution is 120g/L.
Further preferably, in the step S2, the crystal form finishing agent is a compound organosilicon series, and is linear (CH) 3 ) 12 Si 5 O 4 。
Further preferably, in the step S3, in order to accelerate the precipitation effect, especially large particles of the carbide slag, a compound polyacrylamide type aluminum-added precipitator is used, and polyaluminum chloride is compounded with PAM with a cationic molecular weight of 1200-180 ten thousand units according to a mass ratio of 1:2.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is alkaline earth metal molybdate, and the alkaline earth metal molybdate is manganese molybdate, and the amount of the alkaline earth metal molybdate is 6ppm of the mass of formaldehyde.
As shown in fig. 4, fig. 4a shows that the precipitation effect of the solution is good, the supernatant is clear, and the solid-liquid separation is obvious when the compound polyacrylamide precipitant with aluminum is added in step S3; FIG. 4b shows that solid and liquid can be separated by adding anionic polyacrylamide, but the effect is poor, and the supernatant is turbid.
Example 5
A production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding anti-saccharification auxiliary agent and deionized water into formaldehyde solution, then adding carbide slag and n-butyl aldehyde according to reaction
Uniformly adding the mixture for 100-120 minutes to perform condensation reaction, wherein the reaction temperature is 30 ℃;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystal particles to be uniform and enabling the crystallization time to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by secondary filtration, and collecting and treating the filter residue obtained by secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is 0.3:1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is 0.4:1, the molar ratio of formaldehyde to n-butyraldehyde is 3:1.
in the step S1, the mass percentage of the calcium hydroxide in the carbide slag is 65%.
Further preferably, in the step S1, the concentration of the formaldehyde solution is 120g/L.
Further preferably, in the step S2, the crystal form finishing agent is a compound organosilicon series and is a Cyclic (CH) 3 ) 10 Si 5 O 5 。
Further preferably, in step S3, in order to accelerate the precipitation effect of the flocculant, especially large particles of the carbide slag, a compound polyacrylamide type aluminum-added precipitator is used, and the cationic PAM has a molecular weight of 150 ten thousand units.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is alkaline earth metal molybdate, and the alkaline earth metal molybdate is manganese molybdate, and the amount of the alkaline earth metal molybdate is 6ppm of the mass of formaldehyde.
Under the condition of controlling the mass ratio of the carbide slag to the water to be 1:4, n-butyraldehyde is uniformly added in the reaction time of 100 minutes, the concentration of bottom water (formaldehyde content) is changed, and the influence of the adding proportion on the TMP content of the condensation liquid is changed.
TABLE 2
From Table 2, it can be seen that the TMP content of the condensation liquid is increased under the condition that the concentration of the bottom water is gradually increased from 100g/l to 140g/l and the feed ratio is kept unchanged; under the condition of keeping the concentration of the bottom water unchanged, the feeding proportion is increased from 2:1 to 4:1, and the TMP content in the condensation liquid is increased;
example 6
A production method for producing trimethylolpropane by recycling carbide slag is characterized in that carbide slag generated by PVC (polyvinyl chloride) preparation through an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
Preferably, the method comprises the steps of:
s1: adding an anti-saccharification auxiliary agent and deionized water into a formaldehyde solution, then adding carbide slag, uniformly adding n-butyraldehyde into the formaldehyde solution according to the reaction time of 100-120 minutes, and performing condensation reaction, wherein the reaction temperature is 30 ℃;
s2: after the condensation reaction is finished, adding a crystal form finishing agent, wherein the crystal form finishing agent has the function of enabling crystal particles to be uniform and enabling the crystallization time to be uniform;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by secondary filtration, and collecting and treating the filter residue obtained by secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
Further preferably, in the step S1, the weight ratio of the carbide slag to the deionized water is 0.3:1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is (0.4): 1, the molar ratio of formaldehyde to n-butyraldehyde is 3:1.
preferably, in the step S1, the calcium hydroxide in the carbide slag is 64% by mass.
Further preferably, in the step S2, the crystal form finishing agent is a compound organosilicon series, and is linear (CH) 3 ) 12 Si 5 O 4 。
Further preferably, in step S3, in order to accelerate the precipitation effect, especially large particles of the carbide slag, the flocculant is a compound polyacrylamide type aluminum-added precipitator, which is prepared by compounding polyaluminum chloride and nonionic PAM with a molecular weight of 2000 ten thousand units in a mass ratio of 1:1.
Further preferably, in step S1, the formose inhibitor used by the anti-saccharification auxiliary agent is alkaline earth metal molybdate, and the alkaline earth metal molybdate is manganese molybdate, and the amount of the alkaline earth metal molybdate is 6ppm of the mass of formaldehyde.
At a bottom water concentration of 120g/l, formaldehyde: the proportion of n-butyraldehyde is 3:1, and the influence of the mass ratio of carbide slag to deionized water on the TMP content of the primary distillate is realized under the condition that the reaction time is 100 minutes. The mass ratio of the carbide slag to the water is best under the condition of 1:4. The mass ratio of the carbide slag to the water is 1.
TABLE 3
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (7)
1. A production method for producing trimethylolpropane by recycling carbide slag is characterized in that the carbide slag generated by PVC (polyvinyl chloride) preparation by an acetylene method is used as a catalyst and is added into a condensation reaction for preparing trimethylolpropane by using n-butyl aldehyde and formaldehyde as raw materials.
2. The method for producing trimethylolpropane by recycling carbide slag according to claim 1, characterized by comprising the following steps:
s1: adding an anti-saccharification auxiliary agent and deionized water into a formaldehyde solution, then adding carbide slag, uniformly adding n-butyl aldehyde according to the reaction time of 100-120 minutes, and performing condensation reaction, wherein the reaction temperature is 25-47 ℃;
s2: after the condensation reaction is finished, adding a crystal form finishing agent;
s3: adding a flocculating agent into the solution after the reaction to accelerate solid precipitation, filtering and separating solid and liquid after precipitation, and allowing the filtered clear liquid to enter the next step; filtering the filter residue containing a small amount of clear liquid again, recovering the filtrate obtained by the secondary filtration, and collecting and treating the filter residue obtained by the secondary filtration;
the production of producing the trimethylolpropane by recycling the carbide slag is finished.
3. The method according to claim 2, wherein in the step S1, the weight ratio of the carbide slag to the deionized water is (0.2-0.5): 1, the mass ratio of the addition amount of the carbide slag to the n-butyraldehyde is (0.5-3): 1, the molar ratio of formaldehyde to n-butyraldehyde is (1~5): 1.
4. the method as claimed in claim 2, wherein the concentration of the formaldehyde solution in step S1 is 90-150g/L.
5. The method according to claim 2, wherein in step S2, the crystalline form finishing agent is a complex silicone series.
6. The method according to claim 2, wherein in step S3, the flocculating agent is a compound polyacrylamide type aluminum-added precipitating agent.
7. The method according to claim 2, wherein in step S1, the anti-saccharification auxiliary agent is one or a mixture of any two of alkali metal molybdate, alkaline earth metal molybdate, alkali metal tungstate and manganese salt, and the dosage of the anti-saccharification auxiliary agent is 1-10ppm of the mass of the formaldehyde.
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