{ "authors": [], "basis": { "capacity": "2000 t/a distilled acetyl chloride: 1370.0 batches/a of 1459.9 kg in 7920 h on a dedicated train (252.52 kg/h year average), ASSUMED (DESIGN.md D-002, D-003, D-013)", "location": "generic fine-chemicals site with PCl3 and acetic acid supply (not chosen)", "operating_hours_per_year": 7920 }, "benchmarks": [ { "dataset": "acetyl-chloride-by-semi-batch-reaction-of-acetic-acid-with-pcl3-phase-split-and-batch-distillation-2000-t-a", "expression": "product:H3PO3P / product:ACCL", "family": "chlorinated-organics", "kpi": "accl-specific-crude-phosphorous-acid", "no_open_reference": "No open source independent of the dataset found (searched 2026-11-06 as for accl-specific-pcl3): CS 272 248 B2, Example 1, gives 96 g of lower phase per 1.0 mol PCl3 but no acetyl chloride mass, and the dataset's phase split is calibrated to that example, so it is not an independent reference.", "problem": "1 to kg/kg needs core's foundation.units (pip install 'cheme-as-code[units]')", "reference": null, "status": "unchecked", "title": "Crude phosphorous acid (lower phase) per kg of acetyl chloride", "unit": "kg/kg", "value": null }, { "dataset": "acetyl-chloride-by-semi-batch-reaction-of-acetic-acid-with-pcl3-phase-split-and-batch-distillation-2000-t-a", "expression": "feed:PCL3 / product:ACCL", "family": "chlorinated-organics", "kpi": "accl-specific-pcl3", "no_open_reference": "No open source with a plant's or a pilot's PCl3 use per kg of acetyl chloride found (searched 2026-11-06: Google Patents CS 272 248 B2, the dataset's basis, gives charges and the lower phase but no acetyl chloride yield; US 4 209 460 A purifies a crude from another process; US 4 060 546 A names the 1:3 ratio as prior art without a yield; Ullmann's chapters not read, licensed). Only the stoichiometric floor, 0.583 kg/kg, is known.", "problem": "1 to kg/kg needs core's foundation.units (pip install 'cheme-as-code[units]')", "reference": null, "status": "unchecked", "title": "Phosphorus trichloride consumption per kg of acetyl chloride (acetic acid route)", "unit": "kg/kg", "value": null } ], "chemistry": { "inputs": [ { "chemical": "acetic-acid", "grade": null, "inventory_key": "feed:HAC", "note": "Glacial acetic acid (acetic-acid-1, 691 ppm water), 0.826 kg/kg acetyl chloride (stoichiometric 0.765)", "role": "feedstock" }, { "chemical": "phosphorus-trichloride", "grade": null, "inventory_key": "feed:PCL3", "note": "Phosphorus trichloride (no exported library process; proxy P4 + 6 Cl2 recorded, D-012), 0.629 kg/kg acetyl chloride (stoichiometric 0.583)", "role": "feedstock" }, { "chemical": "water", "grade": null, "inventory_key": "feed:PW", "note": "Process water to the vent scrubber, 0.213 kg/kg", "role": "feedstock" }, { "chemical": "nitrogen", "grade": null, "inventory_key": "consumable:nitrogen", "note": "Nitrogen (asu-1) for inerting R-101, the still and the receivers, 10 kg per batch, 6.85 g/kg (ASSUMED)", "role": "feedstock" } ], "outputs": [ { "chemical": "acetyl-chloride", "grade": null, "inventory_key": "product:ACCL", "note": "Distilled acetyl chloride, modelled 99.43 wt% with 0.57 wt% PCl3 (about 1290 ppm P) against a specification of at least 99.0 wt% (US 4 209 460 A), to storage under nitrogen; no source states a purity for this route", "role": "main-product" }, { "chemical": "phosphorous-acid", "grade": null, "inventory_key": "product:H3PO3P", "note": "Crude phosphorous acid (the lower phase), 0.406 kg/kg: 87.5 wt% H3PO3, 10.1 wt% acetic acid, 2.0 wt% acetyl chloride; mass allocation, 28.9 % of the burdens (DESIGN.md D-012)", "role": "co-product" }, { "chemical": "wastewater", "grade": null, "inventory_key": "product:SCRL", "note": "Scrubber bleed, 0.217 kg/kg: 1 wt% HCl, 0.8 wt% acetic acid, to neutralisation", "role": "waste" } ], "utilities": [ { "chemical": "electricity", "grade": null, "inventory_key": "feed:POWER", "note": "0.021 kWh/kg: agitators of R-101 and C-101, reflux pump, scrubber pump and fan (ASSUMED)", "role": "utility" }, { "chemical": "steam", "grade": null, "inventory_key": "feed:LPS", "note": "0.224 kWh/kg of LP steam 350 kPa(a): R-101's tempered-water loop and the still's reboiler at a reflux ratio of 1 with the charge's heat-up (core's still model with its column)", "role": "utility" }, { "chemical": "cooling-water", "grade": null, "inventory_key": "product:CW", "note": "0.232 kWh/kg removed by cooling water: R-101's jacket (from core's semi-batch model), the column's condenser (from core's still model), the product cooler, the residue's cooling", "role": "utility" }, { "chemical": "chilled-water", "grade": null, "inventory_key": "product:BRINE", "note": "0.0014 kWh/kg removed by brine at 258 K: the vent condenser E-103 (the registry has chilled water, not brine: closest entry)", "role": "utility" } ] }, "description": "Glacial acetic acid (acetic-acid-1, 691 ppm water) is charged to an enamelled reactor and\nwarmed to 313 K; phosphorus trichloride (1 mol per 3 mol of acid) is dosed into it over 2 h and\nheld 0.5 h, 3 CH3COOH + PCl3 -> 3 CH3COCl + H3PO3, the batch route of CS 272 248 B2 (Nitrokemia,\nExample 1: below 40 C, then 30 min at 40-50 C). The water of the acid hydrolyses some PCl3; its\nHCl leaves by the vent through a brine condenser, which returns the acetyl chloride vapour, to\na water scrubber. The mixture settles: the lower phase, 87.5 wt% phosphorous acid with acetic\nacid and acetyl chloride, leaves as a crude phosphorous acid co-product (0.41 kg per kg); the\nupper phase is distilled in a batch still with a column of about 10 stages at reflux 1. Product\n99.43 wt% acetyl chloride with 0.57 wt% PCl3 (specification at least 99.0 wt%), which a column\nhardly separates (US 4 209 460 A); the PCl3-rich still residue (46 g per kg) goes to\nincineration. Yield 92.1 % of theory on the acetic acid and the PCl3: a model result, not a\nsourced one (no open source states a yield for this route).\n\nThe batch is modelled with cheme-as-code's semi-batch reactor with a gas vent (reactor:\nsemibatch, batch.vent, core ADRs 0050 and 0054), its batch still with a rectifying column\n(still: with column, ADRs 0055 and 0061) and the batch recipe (process/recipe.yaml with units over several steps, ADRs 0051,\n0052, 0057): the dosing, post-reaction, warming and distillation times come from the models,\nthe reactor is the bottleneck (cycle 5.78 h, 1370 batches a year), the recipe sizes the\nreactor (2.5 m3) and checks its jacket, and the flowsheet's flows are the recipe's year\naverages. The semi-batch and the still write their own duties (ADR 0059), the still's\nreboiler with its reflux and charge's heat-up and its column's condenser (ADRs 0061, 0063),\nand the screening compares the gas a cooling failure releases with R-101's vent (ADR 0058).\nThe phase split is a specified split until core has a liquid-liquid model for these liquids. The\nconversion and the phase split are calibrated to the source's lower phase; the kinetics are\nASSUMED: the PCl3 accumulates to 11.7 % at the end of the dosing and the cooling-failure\ntemperature stays 8.4 K below the boiling point of acetyl chloride; a 100 times slower reaction\nwould exceed it. The vent, sized for 50 m3/h, passes every cooling failure the screening\ncovers, but not the boiling and water-ingress cases, which need a relief study. See DESIGN.md\nfor every assumption.\n", "design_basis": { "assumptions": [ "Route of CS 272 248 B2 (Nitrokemia, 1991), Example 1: PCl3 dosed into acetic acid (1 mol on 3 mol) below 40 C, held at 40-50 C; the mixture settles into an upper acetyl chloride and a lower phosphorous acid phase (D-001, D-004).", "ASSUMED second-order rate law, k 5.5e-4 m3/(kmol s) at 313 K, Ea 50 kJ/mol, sized to the source's 30 min hold; heat of reaction -10.5 kJ/mol derived from CRC formation enthalpies with crystalline H3PO3 (+2.3 with the liquid): the sign is uncertain (D-005).", "ASSUMED conversion of the PCl3 0.95 and the phase split of D101, both calibrated to the lower phase of CS 272 248 B2, Example 1 (D-005, D-006); all HCl leaves the liquid as it forms (batch.vent fraction 1).", "Still: a batch still with a column of 10 theoretical stages at a constant reflux ratio of 1 (US 4 209 460 A, Example 1: a 2 m packed column at 1:1; the stages ASSUMED), core's batch rectification (ADR 0061) at 101.325 kPa(a) on Raoult's law with NIST Antoine constants (an ideal liquid, ASSUMED), to 50 mol% acetyl chloride in the residue (D-007, D-008, D-015).", "All flows are year averages of the recipe (D-003); the duties and power concept estimates (scripts/balance.py, D-006, D-009); accuracy +/-30 % not demonstrated." ], "source": "process/design-basis.yaml" }, "engineering": { "description": "Acetyl chloride from acetic acid and phosphorus trichloride, semi-batch with an HCl vent, phase split and batch distillation, a batch plant, concept stage (issue ChemE-as-Code/process-library#142)", "name": "Acetyl chloride", "requires": "cheme-as-code>=1.10", "stage": "concept", "stages": [ { "id": "concept", "title": "Concept and feasibility" }, { "id": "basic", "title": "Basic engineering" }, { "id": "detail", "title": "Detail engineering" } ], "tool": "plantcode" }, "facets": { "feedstock_basis": [ "fossil", "mineral", "electricity" ], "product_classes": [ "chemicals" ], "region": "generic", "unit_operations": [ "reaction", "separation", "distillation", "absorption" ] }, "families": [ "chlorinated-organics" ], "gap_count": 3, "gates": null, "id": "acetyl-chloride-1", "issues": { "closed_count": 0, "list_url": "https://github.com/ChemE-as-Code/process-library/issues?q=is%3Aissue%20label%3A%22process%3Aacetyl-chloride-1%22", "new": { "action": "https://github.com/ChemE-as-Code/process-library/issues/new?template=1-action-item.yml&labels=process%3Aacetyl-chloride-1&process=acetyl-chloride-1", "change": "https://github.com/ChemE-as-Code/process-library/issues/new?template=4-design-change.yml&labels=process%3Aacetyl-chloride-1&process=acetyl-chloride-1", "hold": "https://github.com/ChemE-as-Code/process-library/issues/new?template=2-engineering-hold.yml&labels=process%3Aacetyl-chloride-1&process=acetyl-chloride-1", "process": "https://github.com/ChemE-as-Code/process-library/issues/new?template=6-process-development.yml&labels=process%3Aacetyl-chloride-1&process=acetyl-chloride-1", "tq": "https://github.com/ChemE-as-Code/process-library/issues/new?template=3-technical-query.yml&labels=process%3Aacetyl-chloride-1&process=acetyl-chloride-1", "tracker": "https://github.com/ChemE-as-Code/process-library/issues/new?template=7-process-tracker.yml&labels=process%3Aacetyl-chloride-1&process=acetyl-chloride-1" }, "open": [], "open_by_gate": {}, "open_count": 0, "private": false, "repository": "ChemE-as-Code/process-library" }, "keywords": [ "acetyl chloride", "acetic acid", "phosphorus trichloride", "PCl3", "phosphorous acid", "acid chloride", "semi-batch", "batch", "dosing", "HCl vent", "vent condenser", "phase separation", "decanter", "batch distillation", "thermal screening", "fine chemicals" ], "lca": { "allocation": "shares", "backend": "factors", "boundary": "cradle-to-gate", "categories": [ { "id": "climate-change", "method": "GWP100", "title": "Climate change", "unit": "kg CO2-eq" } ], "contributions": [], "data_sources": [], "factors_status": "none", "functional_unit": { "amount": 1, "chemical": "acetyl-chloride", "grade": null, "label": "1 kg acetyl chloride", "product": "ACCL", "product_name": "Acetyl chloride", "product_title": "Acetyl chloride to storage", "unit": "kg" }, "goal": "Preliminary gate-to-gate life cycle inventory of acetyl chloride made by dosing phosphorus trichloride into acetic acid in a semi-batch reactor, settling the crude phosphorous acid off as a lower phase and distilling the acetyl chloride at atmospheric pressure, at the concept stage: which raw materials, utilities and wastes the batch plant exchanges per kg of acetyl chloride, as the foreground for a later cradle-to-gate study. No impact results: most backgrounds are not mapped yet (D-012).", "inventory": [ { "direction": "input", "key": "feed:HAC", "kind": "material", "phase": "operation", "provenance": "assumed", "quantity": 0.587549, "title": "Acetic acid (acetic-acid-1)", "unit": "kg" }, { "direction": "input", "key": "feed:PCL3", "kind": "material", "phase": "operation", "provenance": "assumed", "quantity": 0.44755, "title": "Phosphorus trichloride (no library process)", "unit": "kg" }, { "direction": "input", "key": "feed:PW", "kind": "material", "phase": "operation", "provenance": "assumed", "quantity": 0.151747, "title": "Process water (vent scrubber)", "unit": "kg" }, { "direction": "input", "key": "feed:POWER", "kind": "energy", "phase": "operation", "provenance": "assumed", "quantity": 0.0146128, "title": "Electric power", "unit": "kWh" }, { "direction": "input", "key": "feed:LPS", "kind": "energy", "phase": "operation", "provenance": "assumed", "quantity": 0.159539, "title": "LP steam 350 kPa(a)", "unit": "kWh" }, { "direction": "output", "key": "product:ACCL", "kind": "material", "phase": "operation", "provenance": "calculated", "quantity": 1.0, "title": "Acetyl chloride to storage", "unit": "kg" }, { "direction": "output", "key": "product:H3PO3P", "kind": "material", "phase": "operation", "provenance": "assumed", "quantity": 0.406044, "title": "Crude phosphorous acid (lower phase; co-product)", "unit": "kg" }, { "direction": "output", "key": "product:RES", "kind": "material", "phase": "operation", "provenance": "calculated", "quantity": 0.0330287, "title": "Still residue (PCl3 and acetyl chloride) to hazardous-waste incineration", "unit": "kg" }, { "direction": "output", "key": "product:SCRL", "kind": "material", "phase": "operation", "provenance": "calculated", "quantity": 0.154118, "title": "Scrubber liquor (dilute hydrochloric acid) to neutralisation", "unit": "kg" }, { "direction": "output", "key": "product:CW", "kind": "energy", "phase": "operation", "provenance": "assumed", "quantity": 0.165093, "title": "Cooling water return", "unit": "kWh" }, { "direction": "output", "key": "product:BRINE", "kind": "energy", "phase": "operation", "provenance": "assumed", "quantity": 0.000980946, "title": "Chilled brine return (263 K)", "unit": "kWh" }, { "direction": "input", "key": "consumable:nitrogen", "kind": "material", "phase": "operation", "provenance": "assumed", "quantity": 0.00487034, "title": "Nitrogen for inerting R-101, the still and the receivers", "unit": "kg" } ], "no_total": { "baseline": { "climate-change": { "gaps": 10, "reason": "every-contribution-a-gap" } } }, "not_computed": [ "climate-change" ], "pcf": [], "publishable": true, "result": { "classification": "partial", "gaps": 10, "label": "partial screening carbon footprint", "publication": "public" }, "sources": [ "lca/README.md", "lca/dataset.yaml", "lca/factors.yaml", "lca/gaps.csv", "lca/inventory.csv", "lca/lca.yaml", "lca/mappings.yaml", "lca/results.csv", "lca/results.md" ], "totals": { "baseline": {} }, "withheld_reason": null }, "lci_gaps": [ { "dataset": "acetyl-chloride-by-semi-batch-reaction-of-acetic-acid-with-pcl3-phase-split-and-batch-distillation-2000-t-a", "key": "feed:PCL3", "link": "technosphere", "type": "input" }, { "dataset": "acetyl-chloride-by-semi-batch-reaction-of-acetic-acid-with-pcl3-phase-split-and-batch-distillation-2000-t-a", "key": "product:RES", "link": "technosphere", "type": "output" }, { "dataset": "acetyl-chloride-by-semi-batch-reaction-of-acetic-acid-with-pcl3-phase-split-and-batch-distillation-2000-t-a", "key": "product:BRINE", "link": "technosphere", "type": "output" } ], "maintainers": [ { "name": "Artur Schweidtmann" } ], "maturity": "concept", "preliminary": true, "provenance": { "library_commit": "a3c52e472f42fbc8cdacfeacf5ef28703c004174", "previews": { "sheets": [ "BFD", "PFD" ], "source_commit": "a3c52e472f42fbc8cdacfeacf5ef28703c004174", "tool": "cheme 1.6.0 (pyDEXPI 2.1.0)" }, "previews_stale": false, "source_commit": "a3c52e472f42fbc8cdacfeacf5ef28703c004174" }, "publication": { "license": "CC-BY-4.0", "status": "public" }, "references": [ { "title": "Pelyva, J. et al. (Nitrokemia Ipartelepek, 1991) CS 272 248 B2: simultaneous preparation of N-phosphonomethyliminodiacetic acid and C1-4 carboxylic acid chlorides (Example 1: 1.0 mol PCl3 added to 3 mol acetic acid below 40 C, 30 min at 40-50 C, the upper acetyl chloride phase separated; the lower phase, 96 g, phosphorous acid with about 6 % HCl, 2 % acetyl chloride and 10 % acetic acid, used in a phosphonomethylation; no yield or purity of the acetyl chloride)", "url": "https://patents.google.com/patent/CS272248B2/en" }, { "title": "Ohorodnik, A.; Auer, E.; Gehrmann, K. (Hoechst AG, 1980) US 4 209 460 A: Production of pure acetyl chloride (PCl3 hard to distil off; Example 1 without chlorine: a 2 m packed column at reflux 1:1, 125 ppm P to 9 ppm; Examples 2 and 3: chlorine treatment, below 1 ppm P; commercial grade about 98 %, at least 99 % for many uses)", "url": "https://patents.google.com/patent/US4209460A/en" }, { "title": "Blaser, B.; Germscheid, H.-G.; Worms, K.-H. (Henkel, 1977; priority 1961) US 4 060 546 A: Process for the manufacture of acylation products of phosphorous acid (background: PCl3 and anhydrous acetic acid at 1:3; acylation products of phosphorous acid with two P atoms)", "url": "https://patents.google.com/patent/US4060546A/en" }, { "title": "NIST Chemistry WebBook, SRD 69: acetyl chloride, acetic acid, phosphorus trichloride, water (Antoine constants, heats of vaporization, boiling point, liquid heat capacity)", "url": "https://webbook.nist.gov/chemistry/" }, { "title": "PubChem CIDs 6367 (acetyl chloride), 24387 (phosphorus trichloride), 407 (phosphonic acid) (identity; reactions with water, HSDB)", "url": "https://pubchem.ncbi.nlm.nih.gov/" }, { "doi": "10.1002/9783527621606", "title": "Stoessel, F. (2008) Thermal Safety of Chemical Processes, Wiley-VCH (accumulation and MTSR of a semi-batch; method reference, not data)" } ], "repository": { "access": "public", "path": "processes/acetyl-chloride-1", "url": "https://github.com/ChemE-as-Code/process-library" }, "representations": [ { "bytes": 30488, "id": "BFD", "kind": "bfd", "preview": "artifacts/acetyl-chloride-1/BFD.svg", "source": "process/BFD.xml", "status": "preview", "title": "Block flow diagram" }, { "bytes": 92695, "id": "PFD", "kind": "pfd", "preview": "artifacts/acetyl-chloride-1/PFD.svg", "source": "process/PFD.xml", "status": "preview", "title": "Process flow diagram" }, { "id": "process-model", "kind": "process-model", "source": "process/flowsheet.yaml", "status": "viewer", "title": "Flowsheet and stream table" }, { "id": "equipment-list", "kind": "equipment-list", "source": "equipment/equipment-list.yaml", "status": "viewer", "title": "Equipment list" }, { "id": "lca", "kind": "lca", "source": "lca/lca.yaml", "status": "viewer", "title": "Life cycle assessment" } ], "summary": "A batch plant: PCl3 is dosed over 2 h into acetic acid at 313 K, the mixture settles into an upper acetyl chloride and a lower crude phosphorous acid phase, and the upper phase is distilled. Concept stage, 1460 kg per batch every 5.78 h on a dedicated train, thermal screening with a rate-constant sensitivity, preliminary gate-to-gate LCI.", "title": "Acetyl chloride by semi-batch reaction of acetic acid with PCl3, phase split and batch distillation (2000 t/a)", "validation": { "notes": "Concept batch PFD with closed mass, component and element balances (cheme validate, cheme process streams: 3 blocks and 8 steps within tolerance). The semi-batch R101 with its vent (from its ASSUMED rate laws), the batch still ST101 with its column (10 theoretical stages at a reflux ratio of 1, Diwekar's shortcut on Raoult's law with NIST Antoine constants, the ideal liquid ASSUMED; 99.43 wt% acetyl chloride at 98.19 % recovery, 19.2 % of the charge's PCl3 overhead), the scrubber's hydrolysis and the coolers are calculated by cheme process propagate; scripts/balance.py gives the feeds for 2000 t/a, the phase split D101 (calibrated to CS 272 248 B2), the scrubber water, the still's stream temperatures and the duties (no property package of core covers these liquids, no liquid-liquid model applies), except R101's duty and the still's reboiler and condenser, which core's models write (ADRs 0059, 0061, 0063). The vent's acetyl chloride and E-103's load stay script estimates: core 1.10.0's vent vapour carries only the HCl's (DESIGN.md D-015). The recipe's year-average rate of the product agrees with the flowsheet (no cheme.recipe-basis finding); the recipe sizes R-101 (2.5 m3), its jacket check passes against the log-mean cooling-water temperature, and the still's distillation time comes from its boil-up. Thermal screening (cheme process reactor-hazards): dT_ad 21.4 K, accumulation 11.7 %, MTSR 315.8 K against an MTT of 324.15 K (hazard.mtt: the boiling point of acetyl chloride); no criticality class without a TD24 (1 or 2 if the TD24 lies above the MTSR, 5 if below). With k/10 the MTSR is 321.1 K, with k/100 330.5 K, above the MTT (DESIGN.md D-011). At the MTSR a cooling failure releases 0.41 m3/h of gas, at most 31.2 m3/h over the batch (37.9 m3/h at k/100), within R-101's vent capacity of 50 m3/h (ASSUMED); the boiling cases (k/100 above the MTT, a failed warming loop) and water ingress are a design finding for the relief study (DESIGN.md D-014). The heat of reaction's sign is uncertain (D-005). Preliminary gate-to-gate LCI with the per-batch nitrogen, mass allocation to the crude phosphorous acid; the acetic acid linked to acetic-acid-1 and the nitrogen to asu-1, the PCl3 a gap with a recorded proxy, the other backgrounds gaps. cheme maturity reaches no level (assumed feeds, kinetics and separations); the claim `maturity: concept` is the lowest value of the schema, not an evidenced level. Not reviewed. Needs cheme-as-code 1.10.0.", "status": "unreviewed" }, "viewer": { "commit": "a3c52e472f42fbc8cdacfeacf5ef28703c004174", "dirty": false, "sheets": [ "process/BFD.xml", "process/PFD.xml" ], "skipped": [], "snapshot": "snapshots/acetyl-chloride-1/", "stale": false, "tool": "cheme-as-code 1.6.0", "views": [ "checks" ] } }